EP0000700A1 - Metal complexes with a chelating anion comprising a phenolate group, their preparation and their use as light stabilizers, especially for polymeric substances - Google Patents

Abstract

Metal phenolates which have at least one piperidinyl group sterically hindered by nitrogen are suitable as light protection agents for organic material, in particular for higher molecular weight compounds.

Description

The present invention relates to new metal complexes of double or triple charged metal cations with a chelating anion containing phenolate groups, their preparation and use as light stabilizers in organic material, and the organic material protected with the aid thereof.

DT-OS 2,625,967 describes metal complexes with sterically hindered amines and simply charged anions as stabilizers for synthetic polymers. These are mixtures of metal salts and sterically hindered amines.

New metal chelate complexes have now been found which are notable for good sun protection and good extraction stability and are well tolerated in polymers.

worin

• M .ein zweifach oder dreifach positiv geladenes Metallion ist,
• q 2 oder 3 ist, und
• L ein 1 oder 2 Phenolatgruppen enthaltendes t-zähniges chelatbildendes Anion ist, welches mindestens eine Gruppe der Formeln IIa oder IIb
  
  enthält, worin
• t 2, 3 oder 4 ist, und
• R₁,R₂,R₃ und R₄ unabhängig voneinander Alkyl sind, oder
• R₁ und R₃ zusammen Alkylen sind, oder
• R₁ und R₂ bzw. R₃ und R₄ unabhängig voneinander zusammen Alkylen oder Azaalkylen sind, und
• R₅ Wasserstoff, Methyl oder Phenyl bedeutet, und Y Wasserstoff, Oxyl, Alkyl, Alkenyl, Alkinyl, Alkoxyalkyl, Aralkyl, 2,3-Epoxypropyl, eine aliphatische Acylgruppe oder eine der Gruppen -CH₂COOR₆, -CH₂-CH(R₇)-OR₈, -COOR₉ oder -CONHR₉ ist, worin
• R₆ Alkyl, Alkenyl, Phenyl, Aralkyl oder Cycloalkyl ist
• und R₇ Wasserstoff, Methyl oder Phenyl ist, und
• R₈ Wasserstoff, eine aliphatische oder aromatische, eine araliphatische oder alicyclische Acylgruppe bedeutet, worin der aromatische Teil gegebenenfalls mit Chlor, Alkyl, Alkoxy und/oder Hydroxy substitu- iert sein kann, und
• R₉ Alkyl, Cyclohexyl, Phenyl oder Benzyl bedeutet, und R₁₀ ein dreiwertiger und
• R₁₁ ein zweiwertiger organischer Rest ist, wobei R₁₀undR₁₁ den _N-haltigen Ring zu einem 5-, 6- oder 7-gliedrigen Ring ergänzen, und
• r 1 oder 2 und gleich der Anzahl koordinativ gebundener Phenolatanionen im Molekül ist, und
• B ein einfach negativ geladener Ligand ist, und
• s eine ganze Zahl von 0 bis 2 ist, wobei die Summe (q-s)/r + s = q sein muss, und
• m eine ganze Zahl von 0 bis 3 ist, wobei die Summe t·[(p-s)/r] + s + m gleich der Koordinationszahl des Metallions M ist, wobei
• A H₂O oder ein Amin der Formel III
  
  ist, worin
• R₁₂ gegebenenfalls'substituiertes Alkyl, Cycloalkyl, Aryl, Aralkyl, eine gegebenenfalls substituierte Aminoalkylgruppe oder eine Piperidinylgruppe ist, und
• R₁₃ Wasserstoff oder gegebenenfalls substituiertes Alkyl, Cycloalkyl, eine gegebenenfalls substituierte Aminoalkylgruppe oder eine Piperidinylgruppe bedeutet, oder
• R₁₂undR₁₃ zusammen mit dem N-Atom einen durch Alkylgruppen substituierten oder unsubstituierten Pyrrolidin-, Piperidin- oder Morpholinring bilden, und
• -R₁₄ Wasserstoff oder gegebenenfalls substituiertes Alkyl bedeutet.
• R₁, R₂, R₃ und R₄ sind als Alkyl unabhängig voneinander insbesondere Alkyl mit ₁-6 C-Atomen, bevorzugt Aethyl und ganz besonders Methyl.
• R₁ und R₃ sind zusammen als Alkylen insbesondere solches mit 1-6 C-Atomen, vor allem Methylen oder Aethylen.
• R₁ und R₂ bzw. R₃ und R₄ sind zusammen als Alkylen insbesondere geradkettiges oder verzweigtes Alkylen mit 4-8 C-Atomen, vor allem Pentamethylen, und als Azaalkylen insbesondere geradkettiges oder verzweigtes Azaalkylen mit 4-16, vor allem 4-10 C-Atomen, das am N-Atom substituiert sein kann, insbesondere durch einen einwertigen Rest Y, vor allem durch Alkyl, wie solches mit 1-6 C-Atomen,insbesondere Methyl,das aber insbesondere am N-Atom unsubstituiert ist, wie 3-Aza-pentamethylen und insbesondere 2,2,4,4-Tetramethyl-3-aza-pentamethylen, 2,2,3,4,4-Pentamethyl-3-aza-pentamethylen oder das N-oxyl von 2,2,4,4-Tetramethyl-3-aza-pentamethylen. Bevorzugt ist nur eines der Paare R₁/R₂ und R₃/R₄ Alkylen oder Azaalkylen und das andere jeweils Alkyl, und insbesondere sind alle Reste R₁, R₂, R₃ und R₄ Alkyl. R₅ ist insbesondere Wasserstoff oder Methyl.

The new metal complexes correspond to the general formula I

wherein

• M. Is a double or triple positively charged metal ion,
• q is 2 or 3, and
• L is a t-dentate chelating anion containing 1 or 2 phenolate groups, which has at least one group of the formulas IIa or IIb
  
  contains what
• t is 2, 3 or 4, and
• R ₁ , R ₂ , R ₃ and R _{4 are} independently alkyl, or
• R ₁ and R ₃ together are alkylene, or
• R ₁ and R ₂ or R ₃ and R _{4 are} independently alkylene or azaalkylene, and
• R _{5 is} hydrogen, methyl or phenyl, and Y is hydrogen, oxyl, alkyl, alkenyl, alkynyl, alkoxyalkyl, aralkyl, 2,3-epoxypropyl, an aliphatic acyl group or one of the groups -CH ₂ COOR ₆ , -CH ₂ -CH ( R ₇ ) is -OR ₈ , -COOR ₉ or -CONHR ₉ , wherein
• R _{6 is} alkyl, alkenyl, phenyl, aralkyl or cycloalkyl
• and R _{7 is} hydrogen, methyl or phenyl, and
• R ₈ denotes hydrogen, an aliphatic or aromatic, an araliphatic or alicyclic acyl group, in which the aromatic part can optionally be substituted by chlorine, alkyl, alkoxy and / or hydroxy, and
• R _{9 is} alkyl, cyclohexyl, phenyl or benzyl, and R _{10 is} a trivalent and
• R _{11 is} a divalent organic radical, where R ₁₀ and R ₁₁ complement the _N- containing ring to form a 5-, 6- or 7-membered ring, and
• r is 1 or 2 and is equal to the number of coordinatively bound phenolate anions in the molecule, and
• B is a single negatively charged ligand, and
• s is an integer from 0 to 2, where the sum must be (qs) / r + s = q, and
• m is an integer from 0 to 3, the sum t · [(ps) / r] + s + m being the coordination number of the metal ion M, where
• AH ₂ O or an amine of formula III
  
  is what
• R ₁₂ is optionally substituted alkyl, cycloalkyl, aryl, aralkyl, an optionally substituted aminoalkyl group or a piperidinyl group, and
• R _{13 represents} hydrogen or optionally substituted alkyl, cycloalkyl, an optionally substituted aminoalkyl group or a piperidinyl group, or
• R _{12 and} R ₁₃ together with the N atom form a pyrrolidine, piperidine or morpholine ring which is substituted or unsubstituted by alkyl groups, and
• -R _{14 is} hydrogen or optionally substituted alkyl.
• As alkyl, R ₁ , R ₂ , R ₃ and R ₄ are, independently of one another, in particular alkyl having ₁ -6 C atoms, preferably ethyl and very particularly methyl.
• R ₁ and R ₃ together as alkylene are in particular those with 1-6 C atoms, especially methylene or ethylene.
• R ₁ and R ₂ or R ₃ and R ₄ together as alkylene are in particular straight-chain or branched alkylene with 4-8 C atoms, especially pentamethylene, and as azaalkylene in particular straight-chain or branched azaalkylene with 4-16, especially 4- 10 C atoms, which can be substituted on the N atom, in particular by a monovalent radical Y, especially by alkyl, such as those with 1-6 C atoms, in particular methyl, but which is unsubstituted in particular on the N atom, such as 3-aza-pentamethylene and in particular 2,2,4,4-tetramethyl-3-aza-pentamethylene, 2,2,3,4,4-pentamethyl-3-aza-pentamethylene or the N-oxyl of 2,2, 4,4-tetramethyl-3-aza-pentamethylene. Preferably only one of the pairs R ₁ / R ₂ and R ₃ / R _{4 is} alkylene or azaalkylene and the other is in each case alkyl, and in particular all the radicals R ₁ , R ₂ , R ₃ and R _{4 are} alkyl. R ₅ is in particular hydrogen or methyl.

As alkyl, Y is especially one with 1-12 C atoms, preferably α-unbranched, especially with 1-4 C atoms and very particularly methyl.

As an alkenyl, Y is in particular one with 3-12, especially with 3-6 C atoms, such as allyl, methallyl, n-hex-3-enyl, n-oct-4-enyl and n-undec-10-enyl.

As alkynyl, Y is in particular one having 3-6 C atoms, such as propargyl, n _- but-1-ynyl, but-2-ynyl and n-hex-1-ynyl.

If Y is alkoxyalkyl, the alkyl part can contain 1-3 C atoms and the alkoxy part can consist of 1-18 C atoms, such as in methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n- Butoxyethyl, 3-n-butoxyethyl, 2-octoxyethyl or 2-octadecyloxyethyl. Compounds in which Y is an alkoxy group with 2-5 C atoms should be mentioned in particular.

Y is an aralkyl with 7-9 C atoms, e.g. Benzyl or a-phenylethyl.

Y as an aliphatic acyl group is in particular one with 1-4 C atoms, for example formyl, acetyl, acryloyl or crotonyl, in particular acetyl.

If Y is -CH ₂ COOR ₆ , R _{6 is} C ₁ -C ₁₂ alkyl, for example methyl, ethyl, isopropyl, n-butyl, isobutyl, t-butyl, isopentyl, n-octyl, n-decyl or n- Dodecyl; R ₆ is preferably C ₁ -C ₄ alkyl or R ₆ is C ₃ -C ₆ alkenyl, for example allyl, 2-butenyl or 2-hexenyl or C ₇ -C ₈ aralkyl, for example benzyl or α-phenylethyl or finally C ₅ -C ₇ Cycloalkyl, especially cyclohexyl.

If Y is -CH ₂ -CH (R ₇ ) -OR ₈ , R _{7 is} hydrogen, methyl or phenyl, in particular hydrogen. R ₈ is an aliphatic C ₁ -C ₁₈ acyl radical, for example formyl, acetyl, propionyl, butyryl, octanoyl, dodecanoyl, stearoyl or acryloyl. R8 is as aromatic C ₇ acyl residue benzoyl and as araliphatic C ₈ -C ₉ acyl residue, cinnamoyl, phenylacetyl or phenylpropionyl. The aromatic part is optionally substituted with chlorine, C ₁ -C ₄ alkyl, such as methyl, ethyl, n-propyl or t-butyl or with C ₁ -C ₈ alkoxy, such as methoxy, ethoxy, butoxy or octoxy and / or hydroxy. Substituted aromatic acyl groups are, for example, chlorobenzoyl, toluoyl, isopropylbenzoyl, 2,4-dichlorobenzoyl, 4-methoxybenzoyl, 3-butoxybenzoyl, 2-hydroxybenzoyl or 3,5-di-t-butyl-4-hydroxy-benzoyl. An araliphatic substituted acyl group is, for example, β- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl. If R _{8 is} an alicyclic C ₆ -C ₉ acyl group, it can be cyclohexylcarbonyl or 2,4-dimethylcyclohexylcarbonyl. A preferred meaning of R ₈ is also hydrogen.

If Y is the group -COOR ₉ , then R _{9 is} C ₁ -C ₁₂ alkyl, for example methyl, ethyl, isobutyl, t-butyl, n-hexyl, n-octyl, n-decyl or n-dodecyl. Preferred R _{9 are} alkyl groups with 1-4 C atoms.

If Y is -CONHR ₉ , R _{9 is} in particular cyclohexyl or phenyl.

If A is an amine of the formula III, its substituents R ₁₂ , R ₁₃ and R ₁₄ mean, for example, C ₁ -C ₁₈ alkyl, such as methyl, ethyl, isopropyl, sec-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl or n-octadecyl, preferably C ₁ -C ₈ alkyl.

If it is substituted alkyl, it means in particular C ₁ -C ₁₈ hydroxyalkyl, such as 1-hydroxyethyl, 1-hydroxypropyl, 1-hydroxy-1-methyl-ethyl, 3-hydroxy-pentyl, or 1-hydroxy- 2-methyl-ethyl, preferably C ₁ -C ₆ hydroxyalkyl.

R ₁₂ and can also mean C ₅ -C ₁₂ cycloalkyl, which can be, for example, cyclopentyl, cyclohexyl, 4-methylcyclohexyl or 4-tert-butylcyclohexyl. R ₁₂ can also have the meaning of C ₆ -C ₁₈ aryl, which can be, for example, phenyl, tolyl, xylyl, tert-butylphenyl or dodecylphenyl. R ₁₂ as aralkyl can mean -C ₇ -C ₂₀ aralkyl and is, for example, benzyl, 4-methylbenzyl. 4-t-butylbenzyl or 4-dodecylbeazyl, especially benzyl.

Mean R ₁₂ . and R ₁₃ , an optionally substituted aminoalkyl group, it is in particular an aminoalkyl group substituted with a piperidinyl group, for example of the formula IIc

wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₁₀ and Y have the meaning given above and v is an integer from 1 to 8.

R ₁₂ and _{R 13 is} a ridinylgruppe _Pi p _e, so these are preferably one of the formula (IIa) wherein R ₁₀ is a trivalent radical -CH ₂ -CH-CH ₂ -.

R ₁₂ and R ₁₃ together with the N atom of ligand A. can form a pyrrolidine, piperidine or morpholine ring which is substituted or unsubstituted by alkyl groups. In this case it can be, for example, a 2,5-dimethylpyrrolidine, 4-methylpiperidine, 2,2,6,6-tetramethylpiperidine, 2,6-dimethylmorpholine, pyrrolidine, piperidine or morpholine ring, in particular a 2,2,6,6-tetramethylpiperidine ring.

Ligand A is therefore by definition a primary, secondary or tertiary amine which is capable of forming a complex with the metal chelates mentioned above. Examples of such amines are: n-butylamine, n-dodecylamine, β-ethylhexylamine, benzylamine, 4-octylbenzylamine, dibutylamine, dicyclohexylamine, dioctadecylamine, morpholine, 2,2,6,6-tetramethylpiperidine, N-ethylaniline, tri-n- octyiamine, N, N dimethylaniline, N, N-dimethylcyclohexylamine, N-ethylpiperidine, N-methylpyrrolidine, dibenzylpropylamine, N-benzyl-2,5-dimethylpyrrolidine, 4-dimethylamino-2,2,6,6-tetramethylpiperidine, 4 -Dimethylamino-1,2,2,6,6-pentamethyl-piperidine, N, N'-methyl-N, N '- (1,2,2,6,6-pentamethyl-4-piperidyl) ethylene diamine , Hydroxyethylamine, di (hydroxyethyl) amine, tri- (hydroxyethyl) amine, tri- (2-hydroxy-propyl) amine, N-phenyl-N, N-di- (hydroxyethyl) amine or hydroxypropylamine .

The complexes of the formula I according to the invention contain per mole of metal M ^{q +} 0 to 3 moles of the amine ligand A, which is whole or can be partially replaced by water. The mole fraction expressed in formula I with m is therefore composed of the sum of m 'moles of amine ^g and m "moles of water, the mole fractions expressed by m' and m" need not be an integer. Preferred complexes are those with a low water content, since these dissolve better in non-polar polymers than more hydrated complexes. m 'thus assumes approximately the value of m.

A cation M of valence q is, for example, one from the series Mg ²⁺ , Ca ²⁺ , Sr ²⁺ Ba ²⁺ , Zn ²⁺ , Cd ²⁺ , Al ³⁺ , Sn ²⁺ , Cr ³⁺ , Co ²⁺ , Ni ²⁺ , an oxo complex of metal ions, in particular VO ²⁺ and MoO ₂ ²⁺ or a tin alkyl ion of the formula (R *) ₂ Sn ²⁺ , or (CH ₂ CH ₂ COOR *) ₂ Sn ²⁺ , wherein R ^{* is} a C ₁ -C ₈ alkyl, but especially ethyl, n-propyl, n-octyl and especially n-butyl, in particular Ca ²⁺ , Mg ²⁺ , Zn ²⁺ , Co ²⁺ , and especially Ni or Al ³⁺ . The coordination numbers of these cations are known to the person skilled in the art and, depending on the metal, are 4 or 6.

q is 2 or 3, especially 2.

r is 1 or 2 and corresponds to the number of phenolate anions in ligand L. Thus, if a ligand molecule contains several phenolic -OH groups; It depends on the corresponding stability constants and the ratio M / L whether all phenolic OH groups are depratonated and thus contribute to the total charge r ^{- of} the ligand L.

t indicates the denticity of the ligand L with 2, 3 and 4, ie that t describes the number of donor atoms in the molecule which interact directly with the metal center M ^{q +} . There are 2-, 3- and 4-toothed (dentate) ligands for the task in question, the resulting metal complexes being uncharged.

The chelating agent L must meet the condition that it contains at least one of groups IIa or IIb. The symbols R ₁₀ and R ₁₁ have a meaning that the groups IIa and IIb represent, for example, derivatives of pyrrolidine, imidazolidine, 1,4-diazacycloheptanone, piperazine, l-aza-4-thiacyclohexane, dipiperidyl and especially piperidine . Among the numerous piperidines are not only the more easily substituted piperidines in the 4-position, but also spiro compounds such as 1-oxa-3,8-diaza-spiro [4,5] -decane (piperidinespirooxazolidines), 1-oxa-6- aza-spiro [2,5] octane (piperidin-spiro-oxirane), 1,4-dioxa-8-aza-spiro [4,5] -decane and 1,5-dioxa-9-azaspiro [5,5] -undecan ,. as well as the 1- or 4-analog thia or aza compounds of the latter two piperidine-spiro-ketals, and especially 1,3,8-triazaspiro [4,5] -decane (piperidine-spirohydantoins).

ist, worin

• u 0, 1 oder 2 ist, und r oben angegebene Bedeutung hat, und
• R₁₅undR₁₆ unabhängig voneinander Wasserstoff, C₁-C₁₈ Alkyl, welches gegebenenfalls mit einer Gruppe Va, Vb oder Vc:
  
  
• substituiert sein kann; oder eine Gruppe Vc, oder
• eine p-ständige Gruppe der Formel VI
  
• Halogen uder einen Rest -OR₂₄ bedeuten, oder R₁₅ und R₁₆ zusammen einen 1,3-Butadien-1,4-diyl-Rest bilden, wobei
• R₅ und Y die oben angegebene Bedeutung haben, und X₁ und X₂ unabhängig voneinander -O- oder -NR₂₅ sind, und
• R₂₁ Wasserstoff oder C1-C₈ Alkyl ist, und
• R₂₂ Wasserstoff oder eine Gruppe -X₁R₂₆ bedeutet, wobei X₁ die oben angegebene Bedeutung hat, und
• Z -0- oder -O-
  
  - ist, und
• R₂₃ C₁-C₁₈ Alkyl, C₃-C₆ Alkenyl, C₃-C₄ Alkinyl, C₅-C₇ Cycloalkyl, C₆-C₁₀ Aryl, C₇-C₁₄ Aralkyl, ^C ₇-^C ₁₄ Alkylphenyl oder eine Gruppe der Formel VI bedeutet, und
• _R24 Wasserstoff, gegebenenfalls mit einer Gruppe der Formel Vc substituiertes C₁-C₈ Alkyl, C₅-C₇ Cycloalkyl, C₆-C₁₄ Aryl, C₇-C₁₄ Aralkyl, C₂-C₁₂ Alkenyl; oder eine gegebenenfalls mit Chlor, C₁-C₈ Alkyl, C₁-C₈ Alkoxy, einer Gruppe Vc und/oder mit Hydroxy substituierte aliphatische C₁-C₁₈ Acylgruppe, aromatische C₇ Acylgruppe, araliphatische C₈-C₉ Acylgruppe oder alicyclische C₆-C₉ Acylgruppe bedeutet, und
• R₂₅ Wasserstoff, C₁-C₁₈ Alkyl, das gegebenenfalls mit einer Gruppe der Formel Vc substituiert sein kann, C₃-C₆ Alkenyl, C₃-C₄ Alkinyl, C₅-C₇ Cycloalkyl, C₆-C₁₀ Aryl, C₇-C₁₄ Aralkyl, eine Gruppe der Formel CH₂-CH(R₅)-OR₂₆ oder eine Gruppe der Formel _VI bedeutet, und
• R₂₆ Wasserstoff, C₁-C₁₈ Alkyl, C₃-C₆ Alkenyl, Cyclohexyl, Benzyl oder eine gegebenenfalls mit Chlor, C₁-C₈ Alkyl, C₁-C₈ Alkoxy und/oder mit Hydroxy substituierte, aliphatische C₁-C₁₈ Acylgruppe, aroma- tische C₇ Acylgruppe;.araliphatische C₈-C₉ Acylgruppe oder alicyclische C₆-C₉ Acylgruppe bedeutet, und
• R₁₇ Wasserstoff, C₁-C₁₈ Alkyl, Halogen, eine Gruppe -OR₂₄ oder eine Gruppe der Formel Vc bedeutet, und
• R₁₈ eine Gruppe.-N(R₂₅)R₂₇ ist und
• R₁₉ Wasserstoff ist, oder
• R₁₈undR₁₉ zusammen =0 oder =NR₂₇ sind, und
• R₂₀ Wasserstoff, C₇-C₁₄Aralkyl, C₇-C₁₄ Alkylphenyl, oder gegebenenfallss mit einer Gruppe der Formel Vc substituiertes C₁-C₁8 Alkyl, C₂-C₁₂ Alkenyl, C₅-C₁₂ Cycloalkyl oder C₆-C₁₄ Aryl ist, oder,falls R₁₈ und R₁₉ zusammen =0 sind eine Gruppe der Formel Va ist; oder R₂₀ ferner eine Gruppe der Formel _VII
  
  bedeutet, worin R₁₅, R₁₆, R₁₈ und R₁₉ oben angegebene Bedeutung haben, und
• R₂₈ C₁-C₁₂Alkylen, Butenylen, C₆-C₁₀Arylen oder Diphenylen ist, bedeutet, und
• R₂₇ Wasserstoff, C₇-C₁₄ Aralkyl, C₇-C₁₄ Alkylphenyl, Hydroxy, oder gegebenenfalls mit einer Gruppe der Formel Vc substituiertes C₁-C₁₈ Alkyl, C₂-C₁₂ Alkenyl, C₅-C₁₂ Cycloalkyl oderyC₆-C₁₄ Aryl ist, oder eine Gruppe der Formel VI, oder eine Gruppe der Formel -CH₂-CH(R₅)-OR₂₆; oder R₂₇ auch eine Gruppe der Formeln VIIIa oder VIIIb
  
  
  bedeutet, worin R₂₀ die Bedeutung von R₂₀ mit Ausnahme der Gruppen der Formel YII hat, und R₁₅, R₁₆, R₂₅ und R₂₈ dieoben angegebene Bedeutung haben.

Metal complexes of the formula I have proven particularly suitable, in which L ^{r is} a 2-, 3- or 4-toothed chelating agent selected from the class consisting of groups IVA, IVb and IVc

is what

• u is 0, 1 or 2, and r has the meaning given above, and
• R _{15 and} R ₁₆ independently of one another are hydrogen, C ₁ -C ₁₈ alkyl, which may optionally contain a group Va, Vb or Vc:
  
  
• can be substituted; or a group Vc, or
• a p-group of formula VI
  
• Halogen or a radical -OR ₂₄ , or R ₁₅ and R ₁₆ together form a 1,3-butadiene-1,4-diyl radical, where
• R ₅ and Y have the meaning given above, and X ₁ and X _{2 are} independently of one another -O- or -NR ₂₅ , and
• R _{21 is} hydrogen or C1-C ₈ alkyl, and
• R _{22 is} hydrogen or a group -X ₁ R ₂₆ , where X _{1 has} the meaning given above, and
• Z -0- or -O-
  
  - is and
• R ₂₃ C ₁ -C ₁₈ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₄ alkynyl, C ₅ -C ₇ cycloalkyl, C ₆ -C ₁₀ aryl, C ₇ -C ₁₄ aralkyl, ^C ₇ - ^C ₁₄ alkylphenyl or a group of the formula VI, and
• _{R24 is} hydrogen, optionally substituted by a group of the formula Vc, C ₁ -C ₈ alkyl, C ₅ -C ₇ cycloalkyl, C ₆ -C ₁₄ aryl, C ₇ -C ₁₄ aralkyl, C ₂ -C ₁₂ alkenyl; or an aliphatic C ₁ -C ₁₈ acyl group, aromatic C ₇ acyl group, araliphatic C ₈ -C ₉ acyl group or optionally substituted with chlorine, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, a Vc group and / or with hydroxy means C ₆ -C ₉ alicyclic acyl group, and
• R _{25 is} hydrogen, C ₁ -C ₁₈ alkyl, which may optionally be substituted by a group of the formula Vc, C ₃ -C ₆ alkenyl, C ₃ -C ₄ alkynyl, C ₅ -C ₇ cycloalkyl, C ₆ -C ₁₀ aryl , C ₇ -C ₁₄ aralkyl, a group of the formula CH ₂ -CH (R ₅ ) -OR ₂₆ or a group of the formula _V I, and
• R _{26 is} hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₆ alkenyl, cyclohexyl, benzyl or an aliphatic C _{1 which is} optionally substituted by chlorine, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy and / or by hydroxy -C ₁₈ acyl group, aromatic C ₇ acyl group; araliphatic C ₈ -C ₉ acyl group or alicyclic C ₆ -C ₉ acyl group, and
• R _{17 is} hydrogen, C ₁ -C ₁₈ alkyl, halogen, a group -OR ₂₄ or a group of the formula Vc, and
• R _{18 is} a group.-N (R ₂₅ ) R ₂₇ and
• R _{19 is} hydrogen, or
• R _{18 and} R ₁₉ together are = 0 or = NR ₂₇ , and
• R ₂₀ is hydrogen, C ₇ -C ₁₄ aralkyl, C ₇ -C ₁₄ alkylphenyl, or gegebenenfallss with a group of formula Vc substituted C ₁ -C ₁ 8 alkyl, C ₂ -C ₁₂ alkenyl, C ₅ -C ₁₂ cycloalkyl or C ₆ -C _{14 is} aryl, or if R ₁₈ and R ₁₉ together = 0 are a group of the formula Va; or R ₂₀ furthermore a group of formula _VII
  
  means in which R ₁₅ , R ₁₆ , R ₁₈ and R ₁₉ have the meaning given above, and
• R _{28 is} C ₁ -C ₁₂ alkylene, butenylene, C ₆ -C ₁₀ arylene or diphenylene, means, and
• R _{27 is} hydrogen, C ₇ -C ₁₄ aralkyl, C ₇ -C ₁₄ alkylphenyl, hydroxy, or C ₁ -C ₁₈ alkyl, C ₂ -C ₁₂ alkenyl, C ₅ -C ₁₂ cycloalkyl or yC which is optionally substituted by a group of the formula Vc ₆ -C _{14 is} aryl, or a group of formula VI, or a group of formula -CH ₂ -CH (R ₅ ) -OR ₂₆ ; or R ₂₇ also a group of the formulas VIIIa or VIIIb
  
  
  means in which R _{20 has} the meaning of R ₂₀ with the exception of the groups of the formula YII, and R ₁₅ , R ₁₆ , R ₂₅ and R _{28 have the} meaning given above.

• R₅ und Y haben die oben erwähnte Bedeutung.
• u bedeutet 0,1 oder 2, insbesondere 0.

The substituents mentioned in the formulas IVa, IVb, IVc, Va, Vb, Vc, VI, VII, VIIIa and VIIIb above have, for example, the following meaning:

• R ₅ and Y have the meaning mentioned above.
• u means 0, 1 or 2, in particular 0.

If _R15 and _{R16 are} independently of one another C ₁ -C ₁₈ alkyl, it is, for example, methyl, ethyl, isopropyl, n-butyl, t-butyl, amyl, n-hexyl, n-octyl, t-octyl, n -Decyl, n-dodecyl, n-octadecyl or 2-ethyl-hexyl act. Preferred alkyl groups are those with 1-5 C atoms. The alkyl groups can be substituted by a group of the formulas Va, Vb or Vc, preferably Va or Vc; alkyl groups with 1-4 carbon atoms are preferred. Preferred compounds of the formula I are those in which at most one of the radicals R ₁₅ and R ₁₆ is substituted by a group of the formulas Va., Vb or Vc. The radicals -R ₁₅ or R ₁₆ can also be a group Vc.

One of the radicals R ₁₅ and R ₁₆ can be a group of the formula VI Buch. For synthetic reasons, this must be in the p-position to the phenolate oxygen.

If R ₁₅ and R _{16 are} halogen, it can be chlorine or bromine, in particular chlorine.

R ₁₅ and R _{16 are} preferably also hydrogen or -OR ₂₄ .

R ₁₇ as C ₁ -C ₁₈ alkyl is, for example, methyl, ethyl, propyl, butyl, n-hexyz, n-octyl, n-decyl, n-dodecyl or n-octadecyl; alkyl groups with 1-12 C atoms are preferred.

As halogen, R ₁₇ is in particular chlorine.

Also preferred are compounds in which R _{17 is} hydrogen, -OR ₂₄ and in particular a group of the formula Vc.

If R ₂₀ and R _{27 are} C ₇ -C ₁₄ aralkyl, it can be, for example, benzyl, α-phenylethyl or 2-phenylpropyl, in particular benzyl.

R ₂₀ , R _{24 '} R ₂₅ and R _{27 are} C ₁ -C ₁₈ alkyl, for example methyl, ethyl, isopropyl, n butyl, t-butyl, amyl, n-hexyl, n-octyl, t- Octyl, n-decyl, n-dodecyl. Of these, alkyl groups with 1-12 C atoms are preferred. Alkyl groups which are substituted by a group of the formula Vc are also preferred, including in particular those having 1-4 C atoms.

R ₂₀ , R ₂₄ and R ₂₇ are as, C ₂ -C ₁₂ ALkenyl, for example allyl. Amethyally n-hex-3-enyl, n-oct-4-enyl or n-undec-10-enyl. Preference is given to alkenyl groups with 2-6 C atoms, which can optionally be substituted by a group of the formula Vc.

R ₂₀ and R ₂₇ can also mean C ₅ -C ₁₂ cycloalkyl. It is then, for example, cyclopentyl, cyclohexyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl, propylcyclohexyl or dehydroncrhthyl-c-nethyl; especially cyclohexyl.

If R ₂₀ and R _{27 are} cyeloalkyl, they are preferably substituted by a group of the formal Vc.

If R ₂₀ , R ₂₄ and R _{27 are} C ₆ -C ₁₄ aryl, this means, for example, alkylphenyl with 1-8 C atoms, in particular with 1-4 C atoms in the alkyl part, but especially phenyl. The aryl ring is preferably substituted with a group of the formula Vc.

Also preferred are compounds in which one of R ₂₀ and R _{27 is} hydrogen.

R ₂₇ can preferably mean a group of the formula VI.

R ₂₁ is as C ₁ -C ₈ alkyl, for example methyl, ethyl, isopropyl, n-butyl, amyl, n-hexyl or n-octyl. Alkyl groups with 1-4 C atoms are preferred, but in particular R ₂₁ is methyl or hydrogen.

R ₂₃ and -R ₂₆ are as C ₁ -C ₁₈ alkyl, for example methyl, ethyl, isopropyl, n-butyl, t-butyl, amyl; n-hexyl, n-octyl, t-octyl; n-decyl, n-dodecyl; n-octadecyl.

R ₂₃ , R ₂₅ and R ₂₆ are - as C ₃ -C ₆ alkenyl for example. Allyl, methallyl, but-2-enyl, hex-3-enyl, especially allyl.

If R ₂₃ and R _{25 are} C ₃ -C ₄ alkynyl, it is in particular propargyl.

R ₂₃ , R ₂₄ and R ₂₅ are as C ₅ -C ₇ cycloalkyl, for example cyclopentyl, cyclohexyl or methylcyclohexyl, in particular cyclohexyl.

R ₂₃ and R ₂₅ are as C ₆ -C ₁₀ aryl, for example phenyl, α-naphthyl ,. or β-naphthyl, especially phenyl.

If R ₂₃ and R _{25 are} C ₇ -C ₁₄ aralkyl, it is, for example, benzyl, a-phenylethyl or 2-phenylethyl, in particular benzyl.

R ₂₃ is as C ₇ -C ₁₄ alkylphenyl, for example 4-t-butylphenyl or 4-methylphenyl.

R ₂₃ is also preferably a group of the formula VI.

R ₂₄ as C ₇ -C ₁₄ aralkyl is, for example, benzyl, a-phenylethyl or 2-phenylpropyl, in particular benzyl. The aryl radical is preferably substituted with a group of the formula Vc.

R ₂₄ and R ₂₆ are aliphatic C ₁ -C ₁₈ acyl radicals, for example formyl, acetyl, propionyl, butyryl, octanoyl, dodecanoyl, stearoyl or acryloyl. R ₂₄ and R ₂₆ are as aromatic C ₇ acyl radical benzoyl and as araliphatic C ₈ -C ₉ acyl radical, cinnamoyl, phenylacetyl or phenylpropionyl. The aromatic part is optionally with chlorine, C ₁ -C ₄ alkyl, such as methyl, ethyl, n-propyl or t-butyl or with C ₁ -C ₈ Alkozy. such as methoxy, ethoxy, butoxy or octoxy and / or hydroxy. Substituted aromatic acyl groups are, for example

Chlorobenzoyl, toluoyl, isopropylbenzoyl, 2,4-dichlorobenzoyl, 4-methoxybenzoyl, 3-butoxybenzoyl, 2 _- hydroxybenzoyl or 3,5-di-t-butyl-4-hydroxy-benzoyl. An araliphatic substituted acyl group is, for example, β- (3,5-Di-t-butyl-4 _- . Hydroxyphenyl) propionyl. If R ₂₄ and R _{26 are} alicyclic C ₆ -C ₉ acyl groups, it can be cyclohexylcarbonyl or 2,4-dimethylcyclohexylcarbonyl.

A preferred meaning of R ₂₅ is also a group -CH ₂ -CH (R ₅ ) -ßR26

R ₂₈ as C ₁ -C ₁₂ alkylene can be, for example, methylene, dimethylene, trimethylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

R ₂₈ as C ₆ -C ₁₀ arylene means, for example, phenylene or naphthylene.

Although compounds of the formula I which contain up to 4 groups of the formula Va, Vb or VI in the ligand L can also be used industrially, those with 1 or 2 of the groups mentioned are preferred for practical reasons. Further However, nitrogen heterocycles can occur in amine ligand A.

Among the groups Va, Vb and VI occurring in the molecule, those of the formulas Va and VI should be emphasized in particular.

X ₁ in formula Va has the preferred meaning -NR ₂₅ and X ₂ in formula Vc in particular -0-.

worin-

• R₂₉ Alkyl, Alkenyl, Cycloalkyl, Aralkyl oder Aryl ist, und
• R₃₀ Wasserstoff, Alkyl;Alkenyl, Cycloalkyl, Aralkyl, Aryl oder Alkoxycärbonyl-ist, oder
• R₂₉undR₃₀ zusammen gegebenenfalls substituiertes 1,4-Butadi-oder 1,4-Butylew sind, und
• R₃₁ gegebenenfalls substituiertes Alkyl, Alkenyl, Cycloalkyl, Aralkyl, Aryl,Alkoxy oder gegebenenfalls substituiertes Amino bedeutet, und
• R₃₂ Oxo oder gegebenenfalls substituiertes Imino ist.

B as a single-charged anion is, for example, one of an aliphatic or aromatic carboxylic acid, a phosphonic acid half-ester, a phosphinic acid, a phosphinous acid or an enol of the formula IX

wherein-

• R _{29 is} alkyl, alkenyl, cycloalkyl, aralkyl or aryl, and
• R _{30 is} hydrogen, alkyl, alkenyl, cycloalkyl, aralkyl, aryl or alkoxycarbonyl, or
• R _{29 and} R ₃₀ together are optionally substituted 1,4-butadi- or 1,4-butyls, and
• R ₃₁ denotes optionally substituted alkyl, alkenyl, cycloalkyl, aralkyl, aryl, alkoxy or optionally substituted amino, and
• R _{32 is} oxo or optionally substituted imino.

A simply charged anion B of an aliphatic carboxylic acid is in particular an anion of a carboxylic acid R ₃₃ -COOH. wherein R _{33 is} an optionally substituted aliphatic carbon is hydrogen, which is especially alkyl with 1-25, especially 1-12 C atoms, cycloalkyl with 5-12, especially 5-6 C atoms, or alkenyl with 2-25, especially 2-12 C atoms and before represents vinyl, if necessary. are substituted by halogen, in particular chlorine, hydroxy, alkyl having 1-6 C atoms or alkoxy having 1-6 C atoms.

Examples of R ₃₃ are methyl, ethyl, n-hexyl, n-undecyl, 1-ethyl-n-pentyl, cyclopentyl, cyclohexyl, vinyl, allyl or crotonyl, or 4-chlorobutyl.

A simply charged anion B of an aliphatic carboxylic acid is also one of an aliphatic a- or β-aminocarboxylic acid, in particular one having 2-20, especially 2-12, carbon atoms, which is unsubstituted on the amino group, but preferably on the Amino group is mono- or dialkylated, as by branched or in particular straight-chain alkyl having 1-12, especially 1-8 C atoms. Examples of a-aminocarboxylic acids are glycine, α-alanine, valine and isoleucine, which are mono- or disubstituted on the amino group, in particular dnrch-n-alkyl having 1-8 C atoms, such as di-n-octyl; glycine. An example of β-aminocarboxylic acids is β-alanine, which is mono- or disubstituted on the amino group, in particular by n-alkyl having 1-8 C atoms, such as di-n-propyl-β-alanine.

A single-charged anion B of an aromatic carboxylic acid is in particular an anion of a carboxylic acid R ₃₄ -COOH, in which R _{34 is} an optionally substituted aromatic hydrocarbon radical, which is in particular aryl with 6-10 C atoms or aralkyl with 7-14 C atoms. In particular, it can be phenyl, benzyl or phenylethyl, which can be optionally substituted in the aryl part. Substituents in the aryl part are in particular hydroxy, cyclohexyl,

Phenyl, benzyl, α, α-dimethylbenzyl, and in particular C _1-12 alkyl such as methyl, ethyl, iso-propyl, t-butyl, t-octyl or n-dodecyl, especially t-Butyl.Es may be at R ₃₄ therefore for example, 3,5-di-t-butyl-4-hydroxyphenyl-ethyl, 3,5-di-t-butyl-4-hydroxybenzyl or 3,5-di-t-butyl-4-hydroxybenzyl or 3 , 5-Di-t.-butyl-4-hydroxyphenyl act.

oder

worin

• R₃₅ C₁-C₁₈ Alkyl bedeutet, und
• R₃₆ C₁-C₈ Alkyl, Cyelohexyl, gegebenenfalls durch Chlar, C_1-C₄ Alkyl oder Methoxy monosubstituieres C₇-C₁₁ Aralkyl oder Phenyl, C₁-C₄ Alkoxy, Benzoxy, Phenoxy oder Tolyloxy ist, und
• R₃₇undR₃₈ unabhängig voneinander Wasserstoff C₁-C₈Alkyl. Cyclohexyl, gegebenenfalls mit Chlor, C₁-C₄ Alkyl und/oder C₁-C₄Alkoxy mono- oder disubstituiertes C₇-C₁₁ Aralkyl oder Phenyl, oder
• R₃₇undR₃₈ zusammen mit dem N-Atom, an das sie gebunden sind, einen Pyrrolidin-, Piperidin-odsr-iorpholinring bilden, und
• R₃₉ Wasserstoff, C₁-C₆ Alkyl, Phenyl oder 4-Methoxyphenyl ist, und
• R₄₀ Wasserstoff oder Methyl ist, und
• R₄₁undR₄₂ unabhängig voneinander C₁-C₁₂ Alkyl bedeuten.
• R₃₅ ist als C₁-C_18-Alkyl z.B. Methyl, Aethyl, Propyl, n-Butyl, n-Hexyl, n-Octyl, n-Dodecyl, n-Octadecyl; insbesondere C₁-C₄ Alkyl.
• R₃₆, R₃₇ und R₃₈ sind als C₁-C₈ Alkyl z.B. lineare oder verzweigte Alkylgruppen wie Methyl, Aethyl, Propyl, Isopropyl, n-Butyl, n-Hexyl, n-Octyl oder 2-Aethylhexyl, bevorzugt sind C₁-C₄ Alkylgruppen.
• R₃₆, R₃₇ und R₃₈ sind als C₇-C₁₁ Aralkyl, welches gegebenenfalls substituiert sein kann, z.B.Benzyl, 4-Methylbenzyl, 4-Isopropylbenzyl, 3-Chlorbenzyl, 4-Methoxybenzyl oder Phenyläthyl, insbesondere Benzyl.
• ^R _36' R₃₇ und R₃₈ sind als Phenyl, welches gegebenenfalls _sub- stituiert sein kann, beispielsweise Phenyl, 4-Methylphenyl, 3-Chlorphenyl, 4-Methoxyphenyl oder 4-Butoxyphenyl, insbesondere Phenyl.
• R₃₆ ist Als C₁-C₄Alkoxy z.B. Methoxy, Aethoxy, Propoxy oder Butoxy.
• 8₃₇ und R₃₈ können - auch zusäumen mit dem Stickstoffatom, an das sie gebunden sind einen pyrrolidin-, Piperidin- oder Morpholinring, insbesondere einen Piperidin- oder Morpholinring bilden.
• R₃₉ ist als C₁-C₆ Alkyl beispielsweise Methyl, Aethyl, Propyl, n-Butyl, oder n-Hexyl, insbesondere Methyl.

A simply charged anion B of a PhosphonsXure half ester or a phosphinic acid is in particular an anion of a phosphonic acid half ester or a fhosghic acid of the formulas X, XI, XII

or

wherein

• R _{35 is} C ₁ -C ₁₈ alkyl, and
• R _{36 is} C ₁ -C ₈ alkyl, cyelohexyl, optionally chlorine, C ₁ -C ₄ alkyl or methoxy monosubstituted C ₇ -C ₁₁ aralkyl or phenyl, C ₁ -C ₄ alkoxy, benzoxy, phenoxy or tolyloxy, and
• R _{37 and} R _{38 are} independently hydrogen C ₁ -C ₈ alkyl. Cyclohexyl, optionally with chlorine, C ₁ -C ₄ alkyl and / or C ₁ -C ₄ alkoxy mono- or disubstituted C ₇ -C ₁₁ aralkyl or phenyl, or
• R _{37 and} R ₃₈ together with the N atom to which they are attached form a pyrrolidine, piperidine-odsr-iorpholine ring, and
• R _{39 is} hydrogen, C ₁ -C ₆ alkyl, phenyl or 4-methoxyphenyl, and
• R _{40 is} hydrogen or methyl, and
• R _{41 and} R _{42 are} independently C ₁ -C ₁₂ alkyl.
• R ₃₅ is as C ₁ -C ₁₈ alkyl, for example methyl, ethyl, propyl, n-butyl, n-hexyl, n-octyl, n-dodecyl, n-octadecyl; especially C ₁ -C ₄ alkyl.
• R ₃₆ , R ₃₇ and R ₃₈ are as C ₁ -C ₈ alkyl, for example linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, n-hexyl, n-octyl or 2-ethylhexyl, C _{1 being} preferred -C ₄ alkyl groups.
• R ₃₆ , R ₃₇ and R ₃₈ are as C ₇ -C ₁₁ aralkyl, which may optionally be substituted, for example benzyl, 4-methylbenzyl, 4-isopropylbenzyl, 3-chlorobenzyl, 4-methoxybenzyl or phenylethyl, in particular benzyl.
• ^R _{36 'R 37} and R ₃₈ are as stituiert may be phenyl, which is optionally _s UB, for example, phenyl, 4-methylphenyl, 3-chlorophenyl, 4-methoxyphenyl or 4-butoxyphenyl, especially phenyl.
• R ₃₆ is as C ₁ -C ₄ alkoxy, for example methoxy, ethoxy, propoxy or butoxy.
• 8 ₃₇ and R ₃₈ can also - together with the nitrogen atom to which they are attached form a pyrrolidine, piperidine or morpholine ring, in particular a piperidine or morpholine ring.
• R ₃₉ as C ₁ -C ₆ alkyl is, for example, methyl, ethyl, propyl, n-butyl, or n-hexyl, in particular methyl.

Another preferred meaning of R ₃₉ is hydrogen.

^R ₄₁ and R ₄₂ are, as C ₁ -C ₁₂ alkyl, independently of one another, for example methyl, ethyl, isopropyl, t-butyl, amyl, hexyl, t-octyl or n-dodecyl. Alkyl groups with 1-4 C atoms, in particular t-butyl, are preferred.

worin R₄₃ und R₄₄ unabhängig voneinander Alkyl, oder gegebenenfalls mit Chlor, Alkyl und/oder Alkoxy substituiertes Phenyl, Benzyl oder Cyclohexyl bedeuten.A singly charged anion B of a phosphinous acid is in particular an anion of a phosphinous acid of the formula

wherein R ₄₃ and R ₄₄ independently of one another are alkyl, or phenyl, benzyl or cyclohexyl which is optionally substituted by chlorine, alkyl and / or alkoxy.

If R ₄₃ and R ₄₄ are alkyl independently of one another, it is in particular alkyl with 1-18 C atoms, such as methyl, ethyl, n-butyl, n-hexyl, .n-octyl, n-dodetyl or n-octadecyl .

R ₄₃ and R _{44 are} independently phengl, benzyl or cyclohexyl; so these can optionally be mono- or disubstituted with chlorine, C ₁ -C ₄ alkyl and / or C ₁ -C ₄ alkoxy. It can be 4-methoxyphenyl, 3-chlorobenzyl, 4-butylphenyl, 4-methyleyclohexyl or 3-chloro-4-methylphenyl.

If B as a single charged anion is an enol of formula IX, R ₂₉ , R ₃₀ and R ₃₁ as alkyl are in particular alkyl with 1-12 C atoms, especially with 1-6 C atoms, such as methyl, ethyl, n Propyl, n-butyl or n-hexyl.

R _{29 '} ^R ₃₀ and R ₃₁ are alkenyl, in particular alkenyl with 2-12 C atoms, especially 2-6 C atoms, such as allyl, methallyl or n-hex-3-enyl.

R ₂₉ , R ₃₀ and R ₃₁ as cycloalkyl are in particular those having 5-12, especially 5-6, carbon atoms, such as cyclohexyl.

R ₂₉ , R ₃₀ and R ₃₁ are as aralkyl, especially those with 7-12 carbon atoms, such as benzyl or phenylethyl.

^R _{29 '} R ₃₀ and R ₃₁ as aryl are in particular those with 6-10 C atoms, such as phenyl, naphthyl or phenyl, substituted with alkyl with 1-12, in particular 1-4 C atoms, such as methyl, ethyl or butyl; with alkoxy with 1-12, especially 1-4 carbon atoms such as methoxy or butoxy or with halogen such as chlorine.

As alkoxycarbonyl, R ₃₀ is especially one having 2-12, especially 2-6, carbon atoms, such as methoxycarbonyl or ethoxycarbonyl.

Optionally substituted 1,4-butadi-1,3-enylene.As R ₂₉ and R ₃₀ is in particular unsubstituted or one which is a substituent, for example C ₁ -C ₁₂ alkyl, in particular C ₁ -C ₆ alkyl such as methyl; C ₁ -C ₁₂ alkoxy, especially C ₁ -C ₄ alkoxy, such as n-butoxy; or halogen, such as chlorine.

As substituted alkyl, R ₃₁ is in particular one with 1-12, especially 1-6 C atoms, which carries halogen, such as chlorine, as a substituent. - If R _{31 is} alkoxy, it is in particular one with 1-12, especially 1-6, carbon atoms, such as methoxy or ethoxy.

R ₃₁ can represent an amino group; is this substituted,. it is in particular alkylamino with 1-12 C atoms, such as methylamino, dialkylamino with 2-24 C atoms, such as dimethylamino, and especially anilino, which is unsubstituted on the phenyl ring or as a substituent in p-, m- or in particular o-position alkyl with 1-6 C atoms, such as methyl, or in particular alkoxy with 1-6 C atoms, such as methoxy,

Preferred simply charged anions B are especially those of an aliphatic or aromatic carboxylic acid, a phosphonic acid or an enol of the formula IX.

s has the meaning 0 to 2, and is preferably 0.

worin

• M Mg²⁺, VO²⁺, Ca²⁺, Mn²⁺,Zn²⁺, Co²⁺, Ni²⁺ oder A1³⁺ ist, und
• q 2 oder 3 ist, und
• L₁ eine t-zähnige Gruppe der Formel IVa, welche mindestens mit einer Gruppe der Formeln Va, Vb oder VI substituiert ist, bedeutet, und 0,1 oder 2 ist, und 3 ist, und
• R₁₅undR₁₆ unabhängig voneinander Wasserstoff, C₁-C₁₈Alkyl, welches gegebenenfalls mit einer Gruppe der Formeln Va, Vb oder Vc substituiert sein kann; oder eine Gruppe Vc oder eine p-ständige Gruppe der Formel VI. Halogen, oder einen Rest -OR₂₄ bedeuten oder R₁₅ und R₁₆ zusammen einen 1,3-Butadien-1,4-diyl-Rest bilden, wobei
• R₅ Wasserstoff, Methyl oder Phenyl bedeutet, und
• y Wasserstoff, Oxyl, C₁-C₁₂ Alkyl, _C3-C₁₂ Alkenyl, C₃-C₆-Alkinyl, C₂-C₂₁-Alkoxyalkyl, C₇-C₉ Aralkyl, 2,3-Epoxypropyl, eine aliphatische C₁-C₄ Acylgruppe oder eine der Gruppen -CH₂COOR₆, -CH₂-CH(R₇)-OR₈, -COOR₉ oder -CONHR₉ ist, worin
• R₆ C₁-C₁₂ Alkyl, C₃-C₆ Alkenyl, Phenyl, C₇-C₈ Aralkyl oder Cyclohexyl ist und
• R₇ Wasserstoff, Methyl oder Phenyl ist, und
• R₈ Wasserstoff, eine aliphatische C₁-C₁₈ Acylgruppe, eine aromatische C₇ Acylgruppe, eine araliphatische C₈-C₉ Acylgruppe oder eine alicyclische C₆-C₉ Acylgruppe bedeutet, wobei der aromatische Teil gegebenenfalls mit Chlor, C₁-C₄ Alkyl, C₁-C₈ Alkoxy und/oder Hydroxy substituiert sein kann. und
• R₉ C₁-C₁₂ Alkyl, Cyclohexyl, Phenyl oder Benzyl bedeutet, und
• X₁ und X₂ unabhängig voneinander -O-oder -NR₂₅ sind, und R₂₁ .Wasserstoff oder C₁-C₈ Alkyl ist, und
• R₂₂ Wasserstoff oder eine Gruppe -X₁R₂₆ bedeutet, und
• Z -O- oder -O-C- ist, und
• R₂₃ C₁-C₁₈ Alkyl, C₃-C₆ Alkenyl; C₃-C₄ Alkinyl, C₅-C₇ Cycloalkyl, C₆-C₁₀ Aryl, C₇-C₁₄ Aralkyl, ^C ₇-^C ₁₄ Alkylphenyl oder eine Gruppe der Formel VI bedeutet, worin Y und R₂₁ die angegebene Bedeutung haben, und
• R₂₄ Wasserstoff, gegebenenfalls mit einer Gruppe der Formel Vc, worin X₂ und R₂₃ die angegebene Bedeutung hat, substituiertes C₁-C₈ Alkyl, C₅-C₇ Cyclo-. alkyl, C₆-C₁₄ Aryl, C₇-C₁₄ Aralkyl, C₂-C₁₂ Alkenyl; oder eine gegebenenfalls mit Chlor, C₁-C₈ Alkyl, C₁-C₈ Alkoxy, einer Gruppe Vc und/oder mit Hydroxy substituierte aliphatische C₁-C₁₈ Acylgruppe, aromatische C₇ Acylgruppe, araliphatische C₈-C₉ Acylgruppe oder alicyclische C₆-C₉ Acylgruppe bedeutet. und
• R₂₅ Wasserstoff, C₁-C₁₈ Alkyl, das gegebenenfalls mit einer Gruppe der Formel Vc, worin X₂ und R₂₃ die angegebene Bedeutung hat, substituiert sein kann, C₃-C₆ Alkenyl, C₃-C₄ Alkinyl, C₅-C₇ Cycloalkyl, C₆-C₁₀ Aryl, C₇-C₁₄ Aralkyl, eine Gruppe der Formel CH₂-CH(R₅)-OR₂₆ oder eine Gruppe der Formel VI bedeutet, und
• R₂₆ Wasserstoff, C₁-C₁₈ Alkyl, C₃-C₆ Alkenyl, Cyclohexyl, Benzyl oder eine gegebenenfalls mit Chlor, C₁-C₈ Alkyl, C₁-C₈ Alkoxy und/oder mit Hydroxy substituierte aliphatische C₁-C₁₈ Acylgruppe, aromatische C₇ Acylgruppe, araliphatische C₈-C₉ Acylgruppe oder alicyclische C₆-C₉ Acylgruppe bedeutet, und
• r 1 oder 2 ist, und m eine Zahl von 0 bis 3 ist, wobei die Summe (3 q/r)+ gleich der Koordinationszahl des Metallions M ist,
• und A H₂O oder ein Amin der Formel III ist, worin
• R₁₂ gegebenenfalls mit -OH substituiertes C₁-C₁₈ Alkyl, C₅-C₁₂ Cycloalkyl; C₆-C₁₈ Aryl, C₇-C₂₀ Aralkyl. eine gegebenerifalls substituierte Aminoalkylgruppe oder eine Piperidinylgruppe ist, und
• R₁₃ Wasserstoff oder gegebenenfalls mit -OH substituiertes C₁-C₁₈ Alkyl, C₅-C₁₂ Cycloalkyl, eine gege- .benenfalls substituierte Aminoalkylgruppe oder eine Piperidinylgruppe bedautet. oder
• R₁₂undR₁₃ zusammen mit dem N-Atom einen durch Alkylgruppen
  
• R₁₄ Wasserstoff oder gegebenenfalls durch -OH substituiertes C₁-C₁₈ Alkyl bedeutet.

Metal complexes of the formula XIV are preferred

wherein

• M is Mg ²⁺ , VO ²⁺ , Ca ²⁺ , Mn ²⁺ , Zn ²⁺ , Co ²⁺ , Ni ²⁺ or A1 ³⁺ , and
• q is 2 or 3, and
• L _{1 is} a t-toothed group of the formula IVa which is substituted by at least one group of the formulas Va, Vb or VI, and is 0.1 or 2, and is 3, and
• R _{15 and} R ₁₆ independently of one another are hydrogen, C ₁ -C ₁₈ alkyl, which may optionally be substituted with a group of the formulas Va, Vb or Vc; or a group Vc or a p-group of the formula VI. Halogen, or a radical -OR ₂₄ or R ₁₅ and R ₁₆ together form a 1,3-butadiene-1,4-diyl radical, where
• R _{5 is} hydrogen, methyl or phenyl, and
• y hydrogen, oxyl, C ₁ -C ₁₂ alkyl, _C3 -C ₁₂ alkenyl, C ₃ -C ₆ alkynyl, C ₂ -C ₂₁ alkoxyalkyl, C ₇ -C ₉ aralkyl, 2,3-epoxypropyl, an aliphatic C ₁ -C ₄ acyl group or one of the groups -CH ₂ COOR ₆ , -CH ₂ -CH (R ₇ ) -OR ₈ , -COOR ₉ or -CONHR ₉ , wherein
• R _{6 is} C ₁ -C ₁₂ alkyl, C ₃ -C ₆ alkenyl, phenyl, C ₇ -C ₈ aralkyl or cyclohexyl and
• R _{7 is} hydrogen, methyl or phenyl, and
• R _{8 is} hydrogen, an aliphatic C ₁ -C ₁₈ acyl group, an aromatic C ₇ acyl group, an araliphatic C ₈ -C ₉ acyl group or an alicyclic C ₆ -C ₉ acyl group, the aromatic part optionally containing chlorine, C ₁ -C ₄ alkyl, C ₁ -C ₈ alkoxy and / or hydroxy may be substituted. and
• R _{9 is} C ₁ -C ₁₂ alkyl, cyclohexyl, phenyl or benzyl, and
• X ₁ and X _{2 are} independently -O- or -NR ₂₅ , and R _{21 is} hydrogen or C ₁ -C ₈ alkyl, and
• R _{22 represents} hydrogen or a group -X ₁ R ₂₆ , and
• Z is -O- or -OC-, and
• R _{23 is} C ₁ -C ₁₈ alkyl, C ₃ -C ₆ alkenyl; C ₃ -C ₄ alkynyl, C ₅ -C ₇ cycloalkyl, C ₆ -C ₁₀ aryl, C ₇ -C ₁₄ aralkyl, ^C ₇ - ^C ₁₄ alkylphenyl or a group of the formula VI in which Y and R _{21 have} the meaning given have and
• R _{24 is} hydrogen, optionally with a group of the formula Vc, in which X ₂ and R _{23 has} the meaning given, substituted C ₁ -C ₈ alkyl, C ₅ -C ₇ cyclo-. alkyl, C ₆ -C ₁₄ aryl, C ₇ -C ₁₄ aralkyl, C ₂ -C ₁₂ alkenyl; or an aliphatic C ₁ -C ₁₈ acyl group, aromatic C ₇ acyl group, araliphatic C ₈ -C ₉ acyl group or optionally substituted with chlorine, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, a Vc group and / or with hydroxy means alicyclic C ₆ -C ₉ acyl group. and
• R _{25 is} hydrogen, C ₁ -C ₁₈ alkyl, which may optionally be substituted by a group of the formula Vc, in which X ₂ and R _{23 has} the meaning given, C ₃ -C ₆ alkenyl, C ₃ -C ₄ alkynyl, C ₅ -C ₇ cycloalkyl, C ₆ -C ₁₀ aryl, C ₇ -C ₁₄ aralkyl, a group of the formula CH ₂ -CH (R ₅ ) -OR ₂₆ or a group of the formula VI, and
• R _{26 is} hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₆ alkenyl, cyclohexyl, benzyl or an aliphatic C ₁ - which is optionally substituted with chlorine, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy and / or with hydroxy C ₁₈ acyl group, aromatic C ₇ acyl group, araliphatic C ₈ -C ₉ acyl group or alicyclic C ₆ -C ₉ acyl group, and
• r is 1 or 2, and m is a number from 0 to 3, the sum (3 q / r) + being equal to the coordination number of the metal ion M,
• and AH ₂ O or an amine of formula III, wherein
• R ₁₂ is C ₁ -C ₁₈ alkyl optionally substituted with -OH, C ₅ -C ₁₂ cycloalkyl; C ₆ -C ₁₈ aryl, C ₇ -C ₂₀ aralkyl. a given optionally substituted aminoalkyl group or a piperidinyl group, and
• R _{13 is} hydrogen or C ₁ -C ₁₈ alkyl optionally substituted with -OH, C ₅ -C ₁₂ cycloalkyl, an optionally substituted aminoalkyl group or a piperidinyl group. or
• R _{12 and} R ₁₃ together with the N atom are one through alkyl groups
  
• R _{14 is} hydrogen or C ₁ -C ₁₈ alkyl optionally substituted by -OH.

• M Ca²⁺, Mn²⁺, Zn²⁺, Co²⁺, Ni²⁺ oder Al³⁺ ist und
• q 2 oder 3 ist, und
• u 0 ist, und
• L₁ und t oben angegebene Bedeutung haben, wobei
• R₁₅undR₁₆ unabhängig voneinander Wasserstoff, C₁-C₈ Alkyl, welches gegebenenfalls mit einer Gruppe der Formeln Va, Vb oder Vc substituiert sein kann; oder eine Gruppe Vc oder einen Rest -OR₂₄ bedeutet, wobei
• R₅ Wasserstoff oder Methyl ist, und
• R₅ Wasserstoff, C₁-C₄ Alkyl, C₃-C₆ Alkenyl, Propargyl, C₂-C₅ Alköxyalkyl, Benzyl, Acetyl oder eine der Gruppen -CH₂COOR₆, -CH₂CH(R₇)-OR₈, -COOR₉ oder -CONHR₉ ist, worin
• R₆. C₁-C₄ Alkyl ist, und
• R7 Wasserstoff oder Methyl bedeutet, und
• R₈ Wasserstoff bedeutet, und
• R₉ C₁-C₄ Alkyl ist, und
• X₁ und X₂ unabhängig voneinander -O- oder -N-R₂₅ sind, und
• R₂₁ Wasserstoff oder C₁-C₄ Alkyl, und
• R₂₂ und Z oben angegebene Bedeutung haben, und
• R₂₃ C₁-C₁₈ Alkyl, Allyl, Propargyl, Cyclohexyl, Phenyl
• 4-t-Butylphenyl oder eine Gruppe der Formel VI, worin Y und R₂₁ die angegebene Bedeutung hat, und R₂₄ Wasserstoff, gegebenenfalls mit einer Gruppe der Formel Vc, worin X₂ und R₂₃ die angegebene Bedeutung haben, substituiertes C₁-C₁₂ Alkyl, ^C ₂-^C ₆ Alkenyl, Cyclohexyl, Phenyl oder Benzyl bedeutet, und
• R₂₅ Wasserstoff, C₁-C₁₈ Alkyl, das gegebenenfalls mit einer Gruppe der Formel 1Vc, worin X₂ und R₂₃ die angegebene Bedeutung heben, substituiere sein kann, Allyl, Propargyl, Cycichexyl, Phenyl, Benzyl oder eine Gruppe -CH₂-CH(R₅)-OH, worin R₅ die angegebene Bedeutung hat, und
• r und m, sowie die Summe (3 q/r) + m die oben angegebene Bedeutung haben, und
• A H₂0 oder ein Amin der Formel III ist, worin R₁₂undR₁₃ unabhängig voneinander C₁-C₈ Alkyl, C₁-C₆ Hydroxyslkyl oder eine substituierte Aminoalkylgruppe der Formel IId
  
  bedeutet, worin
• v. 1 bis 8 ist, und Y, R₅ und R₂₁ die angegebene Bedeutung hat, oder
• R₁₂undR₁₃ zusammen eine Piperidingruppe bilden, und
• R14 Wasserstoff oder C₁-C₈ Alkyl oder C₁-C₆ Hydroxyalkyl ist.

Among the compounds of the formula XIV, those in which

• M is Ca ²⁺ , Mn ²⁺ , Zn ²⁺ , Co ²⁺ , Ni ²⁺ or Al ³⁺ and
• q is 2 or 3, and
• u is 0, and
• L ₁ and t have the meaning given above, where
• R _{15 and} R ₁₆ independently of one another are hydrogen, C ₁ -C ₈ alkyl, which can optionally be substituted by a group of the formulas Va, Vb or Vc; or a group Vc or a radical -OR ₂₄ , where
• R _{5 is} hydrogen or methyl, and
• R _{5 is} hydrogen, C ₁ -C ₄ alkyl, C ₃ -C ₆ alkenyl, propargyl, C ₂ -C ₅ alkoxyalkyl, benzyl, acetyl or one of the groups -CH ₂ COOR ₆ , -CH ₂ CH (R ₇ ) -OR ₈ , -COOR ₉ or -CONHR ₉ , wherein
• R ₆ . C ₁ -C ₄ alkyl, and
• R7 represents hydrogen or methyl, and
• R _{8 represents} hydrogen, and
• R _{9 is} C ₁ -C ₄ alkyl, and
• X ₁ and X _{2 are} independently -O- or -NR ₂₅ , and
• R _{21 is} hydrogen or C ₁ -C ₄ alkyl, and
• R ₂₂ and Z have the meaning given above, and
• R ₂₃ C ₁ -C ₁₈ alkyl, allyl, propargyl, cyclohexyl, phenyl
• 4-t-butylphenyl group or a group of the formula VI, wherein Y and R ₂₁ has the meaning given, and R ₂₄ is hydrogen, optionally with a group of the formula Vc wherein X ₂ and R ₂₃ have the meaning given, substituted C ₁ - C ₁₂ alkyl, ^C ₂ - ^C ₆ alkenyl, cyclohexyl, phenyl or benzyl, and
• R _{25 is} hydrogen, C ₁ -C ₁₈ alkyl, which may optionally be substituted by a group of the formula 1Vc, in which X ₂ and R _{23 have} the meaning given, allyl, propargyl, cycichexyl, phenyl, benzyl or a group -CH ₂ -CH (R ₅ ) -OH, wherein R _{5 has} the meaning given, and
• r and m, and the sum (3 q / r) + m have the meaning given above, and
• AH _{2 is} 0 or an amine of formula III, wherein R _{12 and} R _{13 are} independently C ₁ -C ₈ alkyl, C ₁ -C ₆ hydroxyl or a substituted aminoalkyl group of formula IId
  
  means what
• v. Is 1 to 8, and Y, R ₅ and R _{21 has} the meaning given, or
• R _{12 and} R ₁₃ together form a piperidine group, and
• R14 is hydrogen or C ₁ -C ₈ alkyl or C ₁ -C ₆ hydroxyalkyl.

• M Ca²⁺, Zn²⁺ oder Ni²⁺ ist, und
• q 2 ist, und
• u 0 ist, und
• L₁ eine t-zähnige Gruppe der Formel IVa, welche mindestens mit einer Gruppe der Formeln Va oder VI substituiert ist, bedeutet und t 2 ist, wobei
• R₁₅ -OR₂₄,mit einer Gruppe Va oder Vc substituiertes
• C₁-C₄ Alkyl oder eine Gruppe Vc bedeutet, und R₁₆ Wasserstoff oder C₁-C₈ Alkyl bedeutet, und
• R₅ Wasserstoff oder Methyl ist, und
• Y Wasserstoff, Methyl oder Acetyl ist, und
• X₁ -NR₂₅ ist, und
• X₂ -O- ist, und
• R₂₁ Wasserstoff oder Methyl ist, und
• R₂₃ eine Gruppe der Formel VI ist und
• R₂₄ mit einer Gruppe der Formel Vc, worin X₂ und R₂₃
• die angegebene Bedeutung haben substituiertes C₁-C₄ Alkyl,bedeutet, und R₂₅ Wasserstoff, C₁-C₁₂ Alkyl, Cyclohexyl, Benzyl,
• Phenyl oder eine Gruppe der Formel -CH₂-CH(R₅)-OH ist, und
• r 1 ist, und
• m 0 bedeutet.

Particularly preferred compounds of the formula XIV are those in which

• M is Ca ²⁺ , Zn ²⁺ or Ni ²⁺ , and
• q is 2, and
• u is 0, and
• L _{1 is} a t-toothed group of the formula IVa which is substituted by at least one group of the formulas Va or VI, and t is 2, where
• R ₁₅ -OR ₂₄ substituted with a group Va or Vc
• C ₁ -C ₄ alkyl or a group Vc, and R _{16 is} hydrogen or C ₁ -C ₈ alkyl, and
• R _{5 is} hydrogen or methyl, and
• Y is hydrogen, methyl or acetyl, and
• X _{1 is} -NR ₂₅ , and
• X _{2 is} -O-, and
• R _{21 is} hydrogen or methyl, and
• R _{23 is} a group of formula VI and
• R ₂₄ with a group of formula Vc, wherein X ₂ and R ₂₃
• have the meaning given substituted C ₁ -C ₄ alkyl, and R _{25 is} hydrogen, C ₁ -C ₁₂ alkyl, cyclohexyl, benzyl,
• Is phenyl or a group of the formula -CH ₂ -CH (R ₅ ) -OH, and
• r is 1, and
• m means 0.

• Beispiele für Verbindungen der Formel XIV sind:
• Der Ni²⁺-1:2 -Komplex des Di-{2-Hydraxy-5-t-octyl-3-[N-methyl-N-(2,2,6,6-tetramethyl-piperidin-4-yl)-amino-methyl]-phenyl}- sulfids.

Of very particular interest are compounds of the formula XIV in which R _{15 is} an o-position C ₁ -C ₄ alkyl group which is substituted by a group of the formula Va and R _{16 is} a p-position 1,1,3,3-tetramethylbutyl- Group is:

• Examples of compounds of the formula XIV are:
• The Ni ²⁺ -1: 2 complex of di- {2-hydraxy-5-t-octyl-3- [N-methyl-N- (2,2,6,6-tetramethyl-piperidin-4-yl) -amino-methyl] -phenyl} - sulfides.

The Ni ²⁺ or Ca ²⁺ -1: 2 complex of di- {2-hydroxy-5-t-octyl- 3- [1,2,2,6,6-pentamethyl-piperidine-4-oxycarbonyl-methyl phenyl} sulfide.

The Zn ²⁺ -1: 1 complex of di- {2-hydroxy-5- [1,2,2,6,6-pentamethyl-piperidin-4-yl] phenyl} sulfide (4-amino-1 , 2,2,6,6-pentamethylpiperidine) ₃ .

The Ni ²⁺ -1: 2 complex of di- {2-hydroxy-5- [2,2,6,6-tetramethylpiperidin-4-yl] phenyl} sulfide.

The Ca ²⁺ or Ni ²⁺ -1: 1 complex of di- {2-hydroxy-5-t-octyl-3- [2,2,6,6-tetramethyl-piperidine-4-oxy-carbonyl-methyl ] -phenyl} sulfide (4-amino-2,2,6,6-tetramethyl-piperidine) ₃ .

The Ni ²⁺ -1: 1 complex of di - {- 2-hydroxy-5-t-octyl-3- [N- (2,3,6-trimethyl-2,6-diethyl-piperidin-4-yl ) -amino] -phenyl} -sulfide (triethanolamine) ₃ .

worin

• M Mg²⁺, VO²⁺, Ca²⁺, Mn²⁺, Zn²⁺, Co²⁺, Ni²⁺ oder Al³⁺ ist, und
• q 2 oder 3 ist, und
• L₂ eine t-zähnige Gruppe der Formel IVb, welche mindestens mit einer Gruppe der Formeln Va, Vb oder VI substituiert ist, bedeutet, und
• t 2 ist, und
• R₁₅undR₁₆ unabhängig voneinander Wasserstoff, C₁-C₁₈ Alkyl, welches gegebenenfalls mit einer Gruppe der Formeln Va, Vb oder Vc substituiert sein kann oder eine Gruppe Vc oder eine p-ständige Gruppe der Formel VI, Halogen oder einen Rest der Formel -OR₂₄ bedeuten oder R₁₅ und R₁₆ zusammen einen 1,3-Butadien-1,4-diyl-Rest bilden, wobei
• R₅ Wasserstoff,. Methyl oder Phenyl bedeutet, und
• Y Wasserstoff, Oxyl, C_l-C₁₂ Alkyl, C₃-C₁₂ Alkenyl, C₃-C₆ ^Alkin^yl, C₂-C₂₁ Alkoxyalkyl, C₇-C₉ Aralkyl, 2,3-Epoxypropyl, eine aliphatische C₁-C₄ Acylgruppe oder eine der Gruppen--CH₂COOR₆, -CH₂-CH(R₇)-OR₈,
• -COOR₉ oder -CONHR₉ ist, worin _R6 C₁-C₁₂ Alkyl, C₃-C₆ Alkenyl, Phenyl, C₇-C₈ Aralkyl oder Cyclohexyl ist und
• R7 Wasserstoff, Methyl oder Phenyl ist, und
• R₈ Wasserstoff, eine aliphatische C₁-C₁₈ Acylgruppe, eine aromatische C₇ Acylgruppe, eine araliphatische C₈-C₉ Acylgruppe oder eine alicyclische C₆-C₉ Acylgruppe bedeutet, wobei der aromatische Teil gege-- benenfalls mit Chlor, C₁-C₄ Alkyl, C₁-C₈ Alkoxy und/oder Hydroxy substituiert sein kann, und
• R₉ C₁-C₁₂ Alkyl, Cyclohexyl, Phenyl oder Benzyl bedeutet, und
• X₁ und X₂ unabhängig voneinander -O- oder -NR₂₅ sind, und R₂₁ Wasserstoff oder C₁-C₈ Alkyl ist, und
• R₂₂ Wasserstoff oder eine Gruppe -X₁R₂₆ bedeutet, und
• Z -O- oder -0-C- ist,und
• R₂₃ C₁-C₁₈ Alkyl, C₃-C₆ Alkenyl, C₃-C₄ Alkinyl, C₅-C₇ Cycloalkyl, C₆-C₁₀ Aryl, C₇-C₁₄ Aralkyl, C₇-C₁₄ Alkylphenyl oder eine Gruppe der Formel VI bedeutet, worin Y und R₂₁ die angegebene Bedeutung haben, und
• R₂₄ Wasserstoff, gegebenenfalls mit einer Gruppe der Formel Vc, worin X₂ und R₂₃ die angegebene Bedeutung hat, substituiertes C₁-C₈ Alkyl, C₅-C₇ C^yclo- alkyl, C₆-C₁₄ Aryl, C₇-C₁₄ Aralkyl, C₂-C₁₂ Alkenyl; oder eine gegebenenfalls mit Chlor, C₁-C₈ Alkyl, C₁-C₈ Alkoxy, einer Gruppe Vc und/oder mit Hydroxy substituierte aliphatische C₁-C₁₈ Acylgruppe, aromatische C₇ Acylgruppe, araliphatische C₈-C₉ Acylgruppe oder alicyclische C₆-C₉ Acylgruppe bedeutet, und
• R₂₅ Wasserstoff, C₁-C₁₈ Alkyl, das gegebenenfalls mit einer Gruppe der Formel Vc, worin X₂ und R₂₃ die angegebene Bedeutung hat, substituiert sein kann, . C₃-C₆ Alkenyl, C₃-C₄ Alkinyl, C₅-C₇ Cycloalkyl, C₆-C₁₀ Aryl, C₇-C₁₄ Aralkyl, eine Gruppe der Formel CH₂-CH(R₅)-OR₂₆ oder eine Gruppe der Formel VI bedeutet, und
• R₂₆ Wasserstoff, C₁-C₁₈ Alkyl, C₃-C₆ Alkenyl, Cyclohexyl, Benzyl oder eine gegebenenfalls mit Chlor, C₁-C₈ Alkyl, C₁-C₈ Alkoxy ^und/oder mit H^ydroxy substituierte aliphatische C₁-C₁₈ Acylgruppe, aromatische C₇ Acylgruppe, araliphatische C₈-C₉ Acylgruppe oder alicyclische C₆-C₉ Acylgruppe bedeutet, und
• R₁₇ Wasserstoff, C₁-C₁₈ Alkyl, Halogen, eine Gruppe -OR₂₄ oder eine Gruppe der Formel Vc, worin R₂₃, R₂₄ und X₂ die angegebene Bedeutung haben, bedeutet, und
• r 1 ist, und
• m eine Zahl von 0 bis 2 ist, wobei die Summe (2-q)+m gleich der Koordinationszahl des Metallions M ist, und
• A H₂O oder ein Amin der Formel III ist, worin
• R₁₂ gegebenenfalls mit -OH substituiertes C₁-C₁₈ Alkyl, C₅-C₁₂ ^{Cycto3? kyl,} C₆-C₁₈ Aryl. C₇-C₂₀ Aralkyl eine gegehenenfalls substituierte Aminoalkylgruppe oder eine Piperidinylgruppe ist, und
• R₁₃ Wasserstoff oder gegebenenfalls mit -OH substituiertes C₁-C₁₈ Alkyl, C₅-C₁₂ Cycloalkyl, eine gegebenenfalls substituierte Aminoalkylgruppe oder eine Piperidinylgruppe bedeutet, oder
• R₁₂undR₁₃ zusammen mit dem N-Atom einen durch Alkylgruppen substituierten oder unsubstituierten Pyrrolidin-, Piperidin- oder Morpholinring bilden, und
• R₁₄ Wasserstoff oder gegebenenfalls mit -OH substituiertes C₁-C₁₈ Alkyl bedeutet.

Metal complexes of the formula XV are also preferred

wherein

• M is Mg ²⁺ , VO ²⁺ , Ca ²⁺ , Mn ²⁺ , Zn ²⁺ , Co ²⁺ , Ni ²⁺ or Al ³⁺ , and
• q is 2 or 3, and
• L _{2 is} a t-toothed group of the formula IVb which is substituted by at least one group of the formulas Va, Vb or VI, and
• t is 2, and
• R _{15 and} R ₁₆ independently of one another are hydrogen, C ₁ -C ₁₈ alkyl, which may optionally be substituted by a group of the formulas Va, Vb or Vc or a group Vc or a p-group of the formula VI, halogen or a radical of the formula -OR ₂₄ or R ₁₅ and R ₁₆ together represent a 1,3 -Butadiene-1,4-diyl residue form, where
• R _{5 is} hydrogen. Means methyl or phenyl, and
• Y is hydrogen, oxyl, C _l -C ₁₂ alkyl, C ₃ -C ₁₂ alkenyl, C ₃ -C ₆ ^A lkin ^y l, C ₂ -C ₂₁ alkoxyalkyl, C ₇ -C ₉ aralkyl, 2,3-epoxypropyl, a aliphatic C ₁ -C ₄ acyl group or one of the groups - CH ₂ COOR ₆ , -CH ₂ -CH (R ₇ ) -OR ₈ ,
• Is -COOR ₉ or -CONHR ₉ , wherein _{R6 is} C ₁ -C ₁₂ alkyl, C ₃ -C ₆ alkenyl, phenyl, C ₇ -C ₈ aralkyl or cyclohexyl and
• R7 is hydrogen, methyl or phenyl, and
• R _{8 represents} hydrogen, an aliphatic C ₁ -C ₁₈ acyl group, an aromatic C ₇ acyl group, an araliphatic C ₈ -C ₉ acyl group or an alicyclic C ₆ -C ₉ acyl group, the aromatic part being optionally with chlorine, C ₁ -C ₄ alkyl, C ₁ -C ₈ alkoxy and / or hydroxy may be substituted, and
• R _{9 is} C ₁ -C ₁₂ alkyl, cyclohexyl, phenyl or benzyl, and
• X ₁ and X _{2 are} independently -O- or -NR ₂₅ , and R _{21 is} hydrogen or C ₁ -C ₈ alkyl, and
• R _{22 represents} hydrogen or a group -X ₁ R ₂₆ , and
• Z is -O- or -0-C-, and
• R ₂₃ C ₁ -C ₁₈ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₄ alkynyl, C ₅ -C ₇ cycloalkyl, C ₆ -C ₁₀ aryl, C ₇ -C ₁₄ aralkyl, C ₇ -C ₁₄ alkylphenyl or a group of the formula VI in which Y and R _{21 have} the meaning given, and
• R ₂₄ is hydrogen, optionally with a group of the formula Vc wherein X ₂ and R ₂₃ has the meaning given, substituted C ₁ -C ₈ alkyl, C ₅ -C ₇ C ^y CLO alkyl, C ₆ -C ₁₄ aryl, C ₇ -C ₁₄ aralkyl, C ₂ -C ₁₂ alkenyl; or an aliphatic C ₁ -C ₁₈ acyl group, aromatic C ₇ acyl group, araliphatic C ₈ -C ₉ acyl group or optionally substituted with chlorine, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, a Vc group and / or with hydroxy means C ₆ -C ₉ alicyclic acyl group, and
• R _{25 is} hydrogen, C ₁ -C ₁₈ alkyl, which may optionally be substituted by a group of the formula Vc, in which X ₂ and R _{23 have} the meaning given,. C ₃ -C ₆ alkenyl, C ₃ -C ₄ alkynyl, C ₅ -C ₇ cycloalkyl, C ₆ -C ₁₀ aryl, C ₇ -C ₁₄ aralkyl, a group of the formula CH ₂ -CH (R ₅ ) -OR ₂₆ or a group of the formula VI, and
• R ₂₆ is hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₆ alkenyl, cyclohexyl, benzyl or an optionally chlorine-, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy ^{and / or} with H ^y droxy substituted aliphatic C ₁ -C ₁₈ acyl group, aromatic C ₇ acyl group, araliphatic C ₈ -C ₉ acyl group or alicyclic C ₆ -C ₉ acyl group, and
• R _{17 is} hydrogen, C ₁ -C ₁₈ alkyl, halogen, a group -OR ₂₄ or a group of the formula Vc, in which R ₂₃ , R ₂₄ and X ₂ have the meaning given, and
• r is 1, and
• m is a number from 0 to 2, the sum (2-q) + m being the coordination number of the metal ion M, and
• AH ₂ O or an amine of formula III, wherein
• R ₁₂ C ₁ -C ₁₈ alkyl optionally substituted with -OH, C ₅ -C ₁₂ ^{Cycto3? kyl,} C ₆ -C ₁₈ aryl. C ₇ -C ₂₀ aralkyl is an optionally substituted aminoalkyl group or a piperidinyl group, and
• R ₁₃ denotes hydrogen or C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl, optionally substituted with -OH, an optionally substituted aminoalkyl group or a piperidinyl group, or
• R _{12 and} R ₁₃ together with the N atom form a pyrrolidine, piperidine or morpholine ring which is substituted or unsubstituted by alkyl groups, and
• R _{14 is} hydrogen or C ₁ -C ₁₈ alkyl optionally substituted with -OH.

• M Ca²⁺, Mn²⁺, Zn²⁺, Co²⁺, Ni²⁺ oder Al²⁺ ist, und
• q 2 oder 3 ist, und
• L₂ und t die oben angegebene Bedeutung haben, wobei
• R₁₅undR₁₆ unabhängig voneinander wasserstoff, C₁-C₈ Alkyl, welches gegebenenfalls mit einer Gruppe der Formeln Va, Vb oder Vc substituiert sein kann; oder eine Gruppe Vc, oder einen Rest -OR₂₄ bedeutet, wobei
• R₅ Wasserstoff oder Methyl ist, und
• Y Wasserstoff, C₁-C₄ Alkyl, C₃-C₆ Alkenyl, Propargyl, C₂-C₅ Alkoxyalkyl, Benzyl, Acetyl oder eine der
• Gruppen -CH₂COOR₃, -CH₂CH(R₇)-OR₈, -COOR₉ oder -CONHR₉ ist, worin
• R₆ C₁-C₄ Alkyl ist, und
• R₇ Wasserstoff oder Methyl bedeutet, und
• R₈ Wasserstoff bedeutet, und
• R₉ C₁-C₄ Alkyl ist, und
• X₁ und X₂ unabhängig voneinander -0- oder -N-R_2S sind, und
• R₂₁ Wasserstoff oder C₁-C₄ Alkyl, und
• R₂₂ und Z oben angegebene Bedeutung haben, und
• R₂₃ C₁-C₁₈ Alkyl, Allyl, Propargyl, Cyclohexyl, Phenyl, 4-t-Butylphenyl oder eine Gruppe der Formel VI,
• worin Y und R₂₁ die angegebene Bedeutung hat, und R₂₄ Wasserstoff, gegebenenfalls mit einer Gruppe der Formel Vc, worin X₂ und R₂₃ die angegebene Bedeutung haben, substituiertes C₁-C₁₂ Alkyl, C₂-C₆ Alkenyl, Cyclohexyl, Phenyl oder Benzyl bedeutet, und
• R₂₅ Wasserstoff, C₁-C₁₂ Alkyl, das gegebenenfalls mit einer Gruppe der Formel Vc, worin X₂ und R₂₃ die angegebene Bedeutung haben; substituiert sein kann, Allyl, Propargyl, Cyclohexyl, Phenyl, Benzyl oder eine Gruppe-CH₂-CH(R₅)-OH, worin R₅ die angegebene 8edeutung hat, und
• R₁₇ Wasserstoff, C₁-C₁₂ Alkyl, einen Rest -OR₂₄ oder eine Gruppe der Formel Vc, worin R₂₃, R₂₄ und X₂ die angegebene Bedeutung haben, und
• r und m, sowie die Summe (2·q)+m die oben angegebene Bedeutung haben, und
• A H₂O oder ein Amin der Formel III ist , worin
• R₁₂ undR₁₃ unabhängig voneinander C₁-C₈ Alkyl, C₁-C₆ Hydroxyalkyl oder eine substituierte Aminoalkylgruppe der Formel IId
  
  bedeutet, worin
• v 1 bis 8 ist, und Y, R₅ und R₂₁ die angegebene Bedeutung haben, oder
• R₁₂undR₁₃ zusammen eine Piperidingruppe bilden, und
• R₁₄ Wasserstoff oder C₁-C₈ Alkyl oder C₁-C₆ Hydroxyalkyl ist.
• Besonders bevorzugte Verbindungen der Formel XV sind solche, in welchen
• _M Ca²⁺, Zn²⁺ oder Ni²⁺ ist, und
• q 2 ist, und
• L₂ eine t-zähnige Gruppe der Formel IVb, welche mindestens mit einer Gruppe der Formeln Va oder VI substituiert ist, bedeutet, und
• t 2 ist, wobei
• R₁₅ Wasserstoff, C₁-C₅ Alkyl, einen Rest -OR₂₄,mit einer Gruppe Va oder Vc substituiertes C₁-C₄ Alkyl oder eine Gruppe Vc bedeutet, und
• R₁₆ Wasserstoff oder C₁-C₈ Alkyl bedeutet,und
• R₁₇ Wasserstoff ist, und
• R₅ Wasserstoff oder Methyl ist, und
• Y Wasserstoff, Methyl oder Acetyl ist, und
• X₁ -N-R₂₅ bedeutet, und
• X₂ -O- ist, und R₂₁ Wasserstoff oder Methyl ist, und
• R₂₃ eine Gruppe der Formel VI bedeutet, und
• R₂₄ mit einer Gruppe der Formel Vc, worin X₂ und R₂₃ die angegebene Bedeutung haben, substituiertes C₁-C₄ Alkyl bedeutet, und
• R₂₅ Wasserstoff, C₁-C₁₂ Alkyl, Cyclohexyl; Benzyl, -CH₂-CH(R₅)-OH ist, und
• r, m, die Summe (2.q)+m, A, R₁₂, R₁₃ und R₁₄ die oben angegebene Bedeutung haben.

Among the compounds of the formula XV, those in which

• M is Ca ²⁺ , Mn ²⁺ , Zn ²⁺ , Co ²⁺ , Ni ²⁺ or Al ²⁺ , and
• q is 2 or 3, and
• L ₂ and t have the meaning given above, where
• R _{15 and} R ₁₆ independently of one another are hydrogen, C ₁ -C ₈ alkyl, which can optionally be substituted by a group of the formulas Va, Vb or Vc; or a group Vc, or a radical -OR ₂₄ , where
• R _{5 is} hydrogen or methyl, and
• Y is hydrogen, C ₁ -C ₄ alkyl, C ₃ -C ₆ alkenyl, propargyl, C ₂ -C ₅ alkoxyalkyl, benzyl, acetyl or one of the
• Groups -CH ₂ COOR ₃ , -CH ₂ CH (R ₇ ) -OR ₈ , -COOR ₉ or -CONHR ₉ , wherein
• R _{6 is} C ₁ -C ₄ alkyl, and
• R _{7 represents} hydrogen or methyl, and
• R _{8 represents} hydrogen, and
• R _{9 is} C ₁ -C ₄ alkyl, and
• X ₁ and X _{2 are} independently -0- or -NR _2S , and
• R _{21 is} hydrogen or C ₁ -C ₄ alkyl, and
• R ₂₂ and Z have the meaning given above, and
• R _{23 is} C ₁ -C ₁₈ alkyl, allyl, propargyl, cyclohexyl, phenyl, 4-t-butylphenyl or a group of the formula VI,
• in which Y and R _{21 have} the meaning given, and R _{24 is} hydrogen, optionally substituted by a group of the formula Vc, in which X ₂ and R _{23 have} the meaning given, C ₁ -C ₁₂ alkyl, C ₂ -C ₆ alkenyl, cyclohexyl , Phenyl or benzyl, and
• R _{25 is} hydrogen, C ₁ -C ₁₂ alkyl, optionally with a group of the formula Vc, in which X ₂ and R _{23 have} the meaning given; may be substituted, allyl, propargyl, cyclohexyl, phenyl, benzyl or a group -CH ₂ -CH (R ₅ ) -OH, in which R _{5 has} the meaning given 8, and
• R _{17 is} hydrogen, C ₁ -C ₁₂ alkyl, a radical -OR ₂₄ or a group of the formula Vc, in which R ₂₃ , R ₂₄ and X _{2 have} the meaning indicated, and
• r and m, and the sum (2 · q) + m have the meaning given above, and
• AH ₂ O or an amine of formula III, wherein
• R _{12 and} R ₁₃ independently of one another are C ₁ -C ₈ alkyl, C ₁ -C ₆ hydroxyalkyl or a substituted aminoalkyl group of the formula IId
  
  means what
• v is 1 to 8, and Y, R ₅ and R _{21 have} the meaning given, or
• R _{12 and} R ₁₃ together form a piperidine group, and
• R _{14 is} hydrogen or C ₁ -C ₈ alkyl or C ₁ -C ₆ hydroxyalkyl.
• Particularly preferred compounds of the formula XV are those in which
• _{M is} Ca ²⁺ , Zn ²⁺ or Ni ²⁺ , and
• q is 2, and
• L _{2 is} a t-toothed group of the formula IVb which is substituted by at least one group of the formulas Va or VI, and
• t is 2, where
• R _{15 is} hydrogen, C ₁ -C ₅ alkyl, a radical -OR ₂₄ , C ₁ -C ₄ alkyl or a group Vc substituted by a group Va or Vc, and
• R _{16 is} hydrogen or C ₁ -C ₈ alkyl, and
• R _{17 is} hydrogen, and
• R _{5 is} hydrogen or methyl, and
• Y is hydrogen, methyl or acetyl, and
• X ₁ denotes -NR ₂₅ , and
• X _{2 is} -O- and R _{21 is} hydrogen or methyl, and
• R _{23 represents} a group of formula VI, and
• R ₂₄ with a group of the formula Vc, in which X ₂ and R _{23 have} the meaning given, is substituted C ₁ -C ₄ alkyl, and
• R _{25 is} hydrogen, C ₁ -C ₁₂ alkyl, cyclohexyl; Is benzyl, -CH ₂ -CH (R ₅ ) -OH, and
• r, m, the sum (2.q) + m, A, R ₁₂ , R ₁₃ and R _{14 have} the meaning given above.

Of particular interest are compounds at formula XV, in which R _{15 is} a C ₁ -C ₄ alkyl group which is O to the hydroxyl group and is substituted by a group of the formula Va or in particular also a group of the formula -OR ₂₄ which is M to the hydroxyl group, in which R _{24 is} a C ₁ -C ₄ alkyl group substituted by a group of the formula Vc. and R ₁₆ and R _{17 are} hydrogen.

Examples of compounds of formula XV are.

The Ni ²⁺ -1: 2 complex of 2- (2'-hydroxy-5'-t-butylphenyl) -5- (N-benzyl-2,2,6,6-tetramethyl-piperidine-4-oxy- carbonyl) benz triazole · (triethanolamine) ₂ .

The Ca ²⁺ -1: 2 complex of 2- {2'-hydroxy-5'-t-buty3.-4 '- [2 * -di- (1,2,2,6,6-pentamethyl-piperidine -4-oxy-carbonyl) hexyl] phenyl} benzotriazals (4-amino-2,2,6,6-tetrametfiyl-piperidins) ₂ .

The Zn ²⁺ -1: 2 complex of 2- {2'-hydroxyef '-sec-butyl)' - 4 '- [2 * - di- (1-acetyl-2,2,6,6-tetramethylpiperidine- 4-oxy-carbonyl) hexyl] phenyl} -4- (1-acetyl-2,2,6,6-tstremethyl-piperidine-4-oxycarbonyl) benzotriazole · (4-dimethyl-amiao-2,2, 6,6-tetramethyl-piperidine) ₂ .

The Ni ²⁺ -1: 2 complex of 2- {2'-hydroxy-3'-sec-butyl) -4 '- [1,2,2,6,6-pen.tamethyl-piperidine-4-oxycarbonylj -phenyl} -benz- triazole. (N, N'-Methyl-N, N '- (1,2,2,6,6-pentamethyl-piperidin-4-yl) ethylenediamine.

worin

• M Mg²⁺, VO²⁺, Ca²⁺, Mn²⁺, Zn²⁺, _Co ²⁺, _Ni²⁺ oder Al³⁺ ist, und
• q 2 oder 3 ist, und
• L₃ eine t-zähnige Gruppe der Formel IVc, welche mindestens mit einer Gruppe der Formeln Va, Vb oder VI substituiert ist, bedeutet, und
• t 2 oder 4 ist, und
• R₁₅undR₁₆ unabhängig voneinander Wasserstoff, C₁-C₁₈ Alkyl, welches gegebenenfalls mit einer Gruppe der Formeln Va, Vb oder Vc substituiert sein kann; oder eine Gruppe Vc,eine p-ständige Gruppe der Formel VI, Halogen oder einen Rest -OR₂₄ bedeuten oder R₁₅ und R₁₆ zusammen einen 1,3-Butadien-1,4-diyl-Rest bilden, wobei
• R₅ Wasserstoff, Methyl oder Phenyl bedeutet, und
• Y Wasserstoff, Oxyl, C₁-C₁₂ Alkyl, C₃-C₁₂ Alkenyl, C₃-C₆ Al^kin^yl, C₂-C₂₁ Alkoxyalkyl, C₇-C₉ Aralkyl, 2,3-Epoxypropyl, eine aliphatische C₁-C₄ Acylgruppe oder eine der Gruppen -CH₂COOR₆, -CH₂-CH(R₇)-OR₈, -COOR₉ oder -CONHR₉ ist, worin
• R₆ C₁-C₁₂ Alkyl, C₃-C₆ Alkenyl, Phenyl, C₇-C₈ Aralkyl oder Cyclohexyl ist und
• R₇ Wasserstoff, Methyl oder Phenyl ist, und
• R₈ Wasserstoff, eine aliphatische C₁-C₁₈ Acylgruppe. eine aromatische C₇ Acylgruppe. eine araliphatische C₈-C₉ Acylgruppe oder eine alicyclische C₆-C₉ Acylgruppe bedeutet, wobei der aromatische Teil gegebenenfalls mit Chlor, C₁-C₄ Alkyl, C₁-C₈ Alkoxy und/oder Hydroxy substituiert sein kann, und
• Rg C₁-C₁₂ Alkyl, Cyclohexyl, Phenyl oder Benzyl bedeutet, und
• X₁ und X₂ unabhängig voneinander -0- oder -NR₂₅ sind, und
• R₂₁ Wasserstoff oder C₁-C₈ Alkyl ist, und
• R₂₂ Wasserstoff oder eine Gruppe -X₁R₂₆ bedeutet, und
• Z -O- oder
  
  ist, und
• R₂₃ C₁-C₁₈ Alkyl, C₃-C₆ Alkenyl, C₃-C₄ Alkinyl, C₅-C₇ Cycloalkyl, C₆-C₁₀ Aryl, C₇-C₁₄ Aralkyl, C₇-C₁₄ Alkylphenyl oder eine Gruppe der Formel VI bedeutet, worin Y und R₂₁ die angegebene Bedeutung haben, und
• R₂₄ Wasserstoff, gegebenenfalls mit einer Gruppe der Formel Vc, worin X₂ und R₂₃ die angegebene Bedeutung hat, substituiertes C₁-C₈ Alkyl, C₅-C₇ Cycloalkyl, C₆-C₁₄ Aryl, C₇-C₁₄ Aralkyl; C₂-C₁₂ Alkenyl; oder eine gegebenenfalls mit Chlor, C₁-C₈ Alkyl, C₁-C₈ Alkoxy, einer Gruppe Vc und/oder mit Hydroxy substituierte aliphatische C₁-C₁₈ Acylgruppe, aromatische C₇ Aeylgruppe, araliphatische C₈-C₉ Acylgruppe oder alicyclische C₆-C₉ Acylgruppe bedeutet und
• R₂₅ Wasserstoff, C₁-C₁₈ Alkyl, das gegebenenfalls mit einer Gruppe der Formel Vc, worin R₂ und R₂₃ die angegebene Bedeutüng hat, substituiert sein kann, C₃-C₆ Alkenyl, C₃-C₄ Alkinyl, C₅-C₇ Cycloalkyl, C₆-C₁₀ Aryl; C₆-C₁₄ Aralkyl, eine Gruppe der Formel CH₂-CH(R₅)-OR₂₆ oder eine Gruppe der Formel VI bedeutet, und
• R₂₆- Wasserstoff, C₁-C₁₈ Alkyl, C₃-C₆ Alkenyl, Cyclohexyl, Benzyl oder eine gegebenenfalls mit Chlor, C₁-C₈ Alkyl, C₁-C₈ Alkoxy und/oder mit Hydroxy substituierte aliphatische C₁-C₁₈ Acylgruppe, aromatische C₇ Acylgruppe. araliphatische C₈-C₉ Acylgruppe oder alicyclische C₆-C₉ Acylgruppe hedeutet, und
• R₁₈ eine Gruppe -N(R₂₅)R₂₇ ist, und
• R₁₉ Wasserwoff ist, oder
• R₁₈undR₁₉ zusammen = oder NR₂₇ sind, und
• R₂₀ Wasserstoff, C₇-C₁₄ Aralkyl, C₇-C₁₄ Alkylphenyl, oder gegebenenfalls mit einer Gruppe der Formel Vc substituiertes C₁-C₁₈ Alkyl, C₂-C₁₂ Alkenyl, C₅-C₁₂ Cycloalkyl oder C₆-C₁₄ Aryl ist, eine Gruppe der Formel VII, oder falls R₁₈ und R₁₉ zusammen ₌0 sind eine Gruppe der Formel Va; wobei X₁, R₂₁ und Y oben definierte Bedeutung haben, und
• R₂₈ C₁-C₁₂ Alkylen, Butenylen, C₆-C₁₀ Arylen oder Diphenylen ist, bedeutet, und
• R₂₇ Wasserstoff, C₇-C₁₄ Aralkyl, C₇-C₁₄ Alkylphenyl, eine Gruppe -OR₂₄, oder gegebenenfalls mit einer Gruppe der Formel Vc substituiertes C₁-C₁₈ Alkyl, C₂-C₁₂ Alkenyl, C₅-C₁₂ Cycloalkyl oder C₆-C₁₄ Aryl ist, oder eine Gruppe der Formel VI, oder eine Gruppe der Formel -CH₂-CH(R₅)-OR₂₆; oder falls R₂₀ nicht eine Gruppe der Formel VII ist; R₂₇ auch eine Gruppe der Formel VIIIa oder VIIIb bedeutet, und
• r 1 oder 2 ist, und
• m eine Zahl von 0 bis 2 ist, wobei die Summe (t·q/r)-m gleich der Koordinationszahl des Metallions M ist, und
• A H₂O oder ein Amin der Formel III ist, worin
• R₁₂ gegebenenfalls mit -OH substituiertes C₁-C₁₈ Alkyl, C₅-C₁₂ Cycloalkyl, C₆-C₁₈ Aralkyl, C₇-C₂₀ Aralkyl, eine gegebenenfalls substituierte Aminoalkylgruppe oder eine Piperidinylgruppe ist, und
• R₁₃ Wasserstoff oder gegebenenfalls mit -OH substituiertes C₁-C₁₈ Alkyl, C₅-C₁₂ Cycloalkyl, eine gegebenenfalls substituierte Aminoalkylgruppe oder eine Piperidinylgruppe bedeutet, oder
• R₁₂undR₁₃ zusammen mit dem N-Atom einen durch Alkylgruppen
• substituierten oder unsubstituierten Pyrrolidin-, Piperidin- oder Morpholinring bilden, und R₁₄ Wasserstoff oder gegebenenfalls mit -OH substituiertes C₁-C₁₈ Alkyl bedeutet.

Metal complexes of the formula XVI are also preferred

wherein

• M is Mg ²⁺ , VO ²⁺ , Ca ²⁺ , Mn ²⁺ , Zn ²⁺ , _Co ²⁺ , _N i ²⁺ or Al ³⁺ , and
• q is 2 or 3, and
• L _{3 is} a t-toothed group of the formula IVc which is substituted by at least one group of the formulas Va, Vb or VI, and
• t is 2 or 4, and
• R _{15 and} R ₁₆ independently of one another are hydrogen, C ₁ -C ₁₈ alkyl, which can optionally be substituted by a group of the formulas Va, Vb or Vc; or a group Vc, a p-group of the formula VI, halogen or a radical -OR ₂₄ or R ₁₅ and R ₁₆ together form a 1,3-butadiene-1,4-diyl radical, where
• R _{5 is} hydrogen, methyl or phenyl, and
• Y is hydrogen, oxyl, C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ alkenyl, C ₃ -C ₆ Al ^{k y} l, C ₂ -C ₂₁ alkoxyalkyl, C ₇ -C ₉ aralkyl, 2,3-epoxypropyl, is an aliphatic C ₁ -C ₄ acyl group or one of the groups -CH ₂ COOR ₆ , -CH ₂ -CH (R ₇ ) -OR ₈ , -COOR ₉ or -CONHR ₉ , wherein
• R _{6 is} C ₁ -C ₁₂ alkyl, C ₃ -C ₆ alkenyl, phenyl, C ₇ -C ₈ aralkyl or cyclohexyl and
• R _{7 is} hydrogen, methyl or phenyl, and
• R _{8 is} hydrogen, an aliphatic C ₁ -C ₁₈ acyl group. an aromatic C ₇ acyl group. is an araliphatic C ₈ -C ₉ acyl group or an alicyclic C ₆ -C ₉ acyl group, where the aromatic part can optionally be substituted by chlorine, C ₁ -C ₄ alkyl, C ₁ -C ₈ alkoxy and / or hydroxy, and
• Rg is C ₁ -C ₁₂ alkyl, cyclohexyl, phenyl or benzyl, and
• X ₁ and X _{2 are} independently -0- or -NR ₂₅ , and
• R _{21 is} hydrogen or C ₁ -C ₈ alkyl, and
• R _{22 represents} hydrogen or a group -X ₁ R ₂₆ , and
• Z -O- or
  
  is and
• R ₂₃ C ₁ -C ₁₈ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₄ alkynyl, C ₅ -C ₇ cycloalkyl, C ₆ -C ₁₀ aryl, C ₇ -C ₁₄ aralkyl, C ₇ -C ₁₄ alkylphenyl or a group of the formula VI in which Y and R _{21 have} the meaning given, and
• R _{24 is} hydrogen, optionally with a group of the formula Vc, in which X ₂ and R _{23 has} the meaning given, substituted C ₁ -C ₈ alkyl, C ₅ -C ₇ cycloalkyl, C ₆ -C ₁₄ aryl, C ₇ -C ₁₄ Aralkyl; C ₂ -C ₁₂ alkenyl; or an aliphatic C ₁ -C ₁₈ acyl group, aromatic C ₇ aeyl group, araliphatic C ₈ -C ₉ acyl group or optionally substituted with chlorine, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, a Vc group and / or with hydroxy C ₆ -C ₉ alicyclic acyl group and
• R _{25 is} hydrogen, C ₁ -C ₁₈ alkyl which may optionally be substituted by a group of the formula Vc in which R ₂ and R _{23 has} the meaning given, C ₃ -C ₆ alkenyl, C ₃ -C ₄ alkynyl, C ₅ -C ₇ cycloalkyl, C ₆ -C ₁₀ aryl; C ₆ -C ₁₄ aralkyl, a group of the formula CH ₂ -CH (R ₅ ) -OR ₂₆ or a group of the formula VI, and
• R ₂₆ - hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₆ alkenyl, cyclohexyl, benzyl or an aliphatic C ₁ optionally substituted with chlorine, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy and / or with hydroxy -C ₁₈ acyl group, aromatic C ₇ acyl group. araliphatic C ₈ -C ₉ acyl group or alicyclic C ₆ -C ₉ acyl group, and
• R _{18 is} a group -N (R ₂₅ ) R ₂₇ , and
• R _{19 is} Wasserwoff, or
• R _{18 and} R ₁₉ together = or NR ₂₇ , and
• R _{20 is} hydrogen, C ₇ -C ₁₄ aralkyl, C ₇ -C ₁₄ alkylphenyl, or C ₁ -C ₁₈ alkyl, C ₂ -C ₁₂ alkenyl, C ₅ -C ₁₂ cycloalkyl or C _{6 which is} optionally substituted by a group of the formula Vc -C _{14 is} aryl, a group of the formula VII, or if R ₁₈ and R ₁₉ together ₌ 0 are a group of the formula Va; where X ₁ , R ₂₁ and Y have the meaning defined above, and
• R _{28 is} C ₁ -C ₁₂ alkylene, butenylene, C ₆ -C ₁₀ arylene or diphenylene, means, and
• R _{27 is} hydrogen, C ₇ -C ₁₄ aralkyl, C ₇ -C ₁₄ alkylphenyl, a group -OR ₂₄ , or C ₁ -C ₁₈ alkyl optionally substituted by a group of the formula Vc, C ₂ -C ₁₂ alkenyl, C ₅ - C _{12 is} cycloalkyl or C ₆ -C ₁₄ aryl, or a group of the formula VI, or a group of the formula -CH ₂ -CH (R ₅ ) -OR ₂₆ ; or if R _{20 is} not a group of formula VII; R ₂₇ also denotes a group of the formula VIIIa or VIIIb, and
• r is 1 or 2, and
• m is a number from 0 to 2, the sum (t * q / r) -m being the coordination number of the metal ion M, and
• AH ₂ O or an amine of formula III, wherein
• R ₁₂ is C ₁ -C ₁₈ alkyl optionally substituted with -OH, C ₅ -C ₁₂ cycloalkyl, C ₆ -C ₁₈ aralkyl, C ₇ -C ₂₀ aralkyl, an optionally substituted aminoalkyl group or a piperidinyl group, and
• R ₁₃ denotes hydrogen or C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl, optionally substituted with -OH, an optionally substituted aminoalkyl group or a piperidinyl group, or
• R _{12 and} R ₁₃ together with the N atom are one through alkyl groups
• form substituted or unsubstituted pyrrolidine, piperidine or morpholine ring, and R _{14 is} hydrogen or C ₁ -C ₁₈ alkyl optionally substituted with -OH.

• M Ca²⁺, Mn²⁺, Zn²⁺, Co²⁺, Ni²⁺ oder Al³⁺ ist, und
• q 2 oder 3 ist, und
• t 2 ist
• L₃ oben angegebene Bedeutung hat, wobei
• R₁₅undR₁₆ unabhängig voneinander Wasserstoff, C₁-C₈ Alkyl, welches gegebenenfalls mit einer Gruppe der Formeln Va, Vb oder Vc substituiert sein kann; oder eine Gruppe Vc oder einen Rest -OR₂₄ bedeutet, wobei
• R₅ Wasserstoff oder Methyl ist, und
• Y Wasserstoff, C₁-C₄ Alkyl, C₃-C₆ Alkenyl, Propargyl, C₂-C₅ Alkoxyalkyl, Benzyl, Acetyl oder eine der Gruppen -CH₂COOR₆, -CH₂CH(R₇)-OR₈, -COOR₉ oder -CONHR₉ ist, worin
• R₆ C₁-C₄ Alkyl ist, und
• R₇ Wasserstoff oder Methyl edeutet, und
• R₈ Wasserstoff bedeutet, und
• R₉ C₁-C₄ Alkyl ist, und
• X₁ und X₂ unabhängig voneinander -0- oder -N-R₂₅ sind, und
• R₂₁ Wasserstoff oder C₁-C₄ Alkyl, und
• R₂₂ und Z oben angegebene Bedeutung haben, und
• R₂₃ C₁-C₁₈ Alkyl, Allyl, Propargyl, Cyclohexyl, Phenyl, 4-t-Butylphenyl oder eine Gruppe der Formel VI, worin ^Y und R₂₁ die angegebene Bedeutung hat, und
• R₂₄ Wasserstoff, gegebenenfalls mit einer Gruppe der Formel Vc, worin X₂ und R₂₃ die angegebene Bedeutung haben, substituiertes C₁-C₁₂ Alkyl, ^C ₂-^C ₆ Alkenyl, Cyclohexyl, Phenyl oder Benzyl bedeutet, und
• R₂₅ Wasserstoff, C₁-C₁₂ Alkyl, das gegebenenfalls mit einer Gruppe der Formel Vc, worin X₂ und R₂₃ die angegebene Bedeutung haben, substituiert sein kann, Allyl, Propargyl, Cyclohexyl, Phenyl, Benzyl oder eine Gruppe -CH₂-CH(R₅)-OH, worin R₅ die angegebene Bedeutung hat, und
• R₁₈ eine Gruppe -N(R₂₅)R₂₇ ist, und
• ^R ₁₉ Wasserstoff ist, oder
• R₁₈undR₁₉ zusammen =O oder =NR₂₇ sind, und
• R₂₀ Wasserstoff, oder gegebenenfalls mit einer Gruppe der Formel Vc substituiertes C_I-C₁₂ Alkyl, C₂-C₆ Alkenyl, Cyclohexyl oder Phenyl ist, und falls R₁₈ R₁₉ zusammen =0 sind, eine Gruppe der Formel Va ist, und
• R₂₇ Wasserstoff, oder gegebenenfalls mit einer Gruppe der Formel Vc substituiertes C₁-C₁₂ Alkyl, C₂-^C ₆ Alkenyl, Cyclohexyl oder Phenyl; oder eine Gruppe der Formel VI bedeutet, und
• r 1 ist, und
• m eine Zahl von 0 bis 2- ist, wobei die Summe (2·q)+m gleich der Koordinationszahl des Metallions M ist, und
• A H₂O oder ein Amin der Formel III ist, worin
• R₁₂undR₁₃ unabhängig voneinander C₁-C₈ Alkyl, C₁-C₆ Hydroxyalkyl oder eine substituierte Aminoalkylgruppe der Formel IId
  
  bedeutet, worin
• v 1 bis 8 ist, und Y, R₅ und R₂₁ die angegebene Bes deutung hat, oder
• R₁₂undR₁₃ zusammen eine Piperidingruppe bilden, und
• R₁₄ Wasserstoff oder C₁-C₈ Alkyl oder C₁-C₆ Hydroxyalkyl ist.

Among the compounds of the formula XVI, mention should be made of those in which

• M is Ca ²⁺ , Mn ²⁺ , Zn ²⁺ , Co ²⁺ , Ni ²⁺ or Al ³⁺ , and
• q is 2 or 3, and
• t is 2
• L ₃ has the meaning given above, where
• R _{15 and} R ₁₆ independently of one another are hydrogen, C ₁ -C ₈ alkyl, which can optionally be substituted by a group of the formulas Va, Vb or Vc; or a group Vc or a radical -OR ₂₄ , where
• R _{5 is} hydrogen or methyl, and
• Y is hydrogen, C ₁ -C ₄ alkyl, C ₃ -C ₆ alkenyl, propargyl, C ₂ -C ₅ alkoxyalkyl, benzyl, acetyl or one of the groups -CH ₂ COOR ₆ , -CH ₂ CH (R ₇ ) -OR ₈ , -COOR ₉ or -CONHR ₉ , wherein
• R _{6 is} C ₁ -C ₄ alkyl, and
• R _{7 represents} hydrogen or methyl, and
• R _{8 represents} hydrogen, and
• R _{9 is} C ₁ -C ₄ alkyl, and
• X ₁ and X _{2 are} independently -0- or -NR ₂₅ , and
• R _{21 is} hydrogen or C ₁ -C ₄ alkyl, and
• R ₂₂ and Z have the meaning given above, and
• R ₂₃ C ₁ -C ₁₈ alkyl, allyl, propargyl, cyclohexyl, phenyl, 4-t-butylphenyl or a group of the formula VI, in which ^Y and R _{21 have} the meaning given, and
• R ₂₄ is hydrogen, optionally with a group of the formula Vc wherein X ₂ and R ₂₃ have the meaning given, substituted C ₁ -C ₁₂ alkyl, ^C ₂ - ^C ₆ alkenyl, cyclohexyl, phenyl or benzyl, and
• R _{25 is} hydrogen, C ₁ -C ₁₂ alkyl, which may optionally be substituted by a group of the formula Vc, in which X ₂ and R _{23 have} the meaning given, allyl, propargyl, cyclohexyl, phenyl, benzyl or a group -CH ₂ -CH (R ₅ ) -OH, wherein R _{5 has} the meaning given, and
• R _{18 is} a group -N (R ₂₅ ) R ₂₇ , and
• ^R _{19 is} hydrogen, or
• R _{18 and} R ₁₉ together are = O or = NR ₂₇ , and
• R _{20 is} hydrogen, or C _I -C ₁₂ alkyl, C ₂ -C ₆ alkenyl, cyclohexyl or phenyl which is optionally substituted by a group of the formula Vc, and if R ₁₈ R ₁₉ together = 0 is a group of the formula Va, and
• R ₂₇ is hydrogen, or optionally substituted with a group of formula Vc C ₁ -C ₁₂ alkyl, C ₂ - ^C ₆ alkenyl, cyclohexyl or phenyl; or a group of the formula VI, and
• r is 1, and
• m is a number from 0 to 2, the sum (2 * q) + m being the coordination number of the metal ion M, and
• AH ₂ O or an amine of formula III, wherein
• R _{12 and} R ₁₃ independently of one another are C ₁ -C ₈ alkyl, C ₁ -C ₆ hydroxyalkyl or a substituted aminoalkyl group of the formula IId
  
  means what
• v is 1 to 8, and Y, R ₅ and R _{21 has} the meaning given, or
• R _{12 and} R ₁₃ together form a piperidine group, and
• R _{14 is} hydrogen or C ₁ -C ₈ alkyl or C ₁ -C ₆ hydroxyalkyl.

• M Ca²⁺, Zn²⁺ oder Ni²⁺ ist, und
• q 2 ist, und
• L eine t-zähnige Gruppe der Formel IVc, welche mindestens mit einer Gruppe der Formel VI substituiert ist, bedeutet, und
• t 2 ist, wobei
• R₁₅undR₁₆ Wasserstoff sind, und
• R₁₈ eine Gruppe -N(R₂₅)R₂₇ ist, worin
• R₂₅ Wasserstoff, C₁-C₁₂ Alkyl oder eine Gruppe -CH₂-CH(R₅)-OH, worin R₅ Wasserstoff oder Methyl ist, bedeutet, und
• R₂₇ Wasserstoff, oder mit einer Gruppe der Formel Vc substituiertes C₁-C₄ Alkyl oder eine Gruppe der Formel VI bedeutet, wobei
• ^X ₂ -0- ist, und
• Y Wasserstoff, Methyl oder Acetyl bedeutet, und
• R₂₁ Wasserstoff oder Methyl ist, und
• ^R23 eine Gruppe der Formel VI ist, und
• _R19 Wasserstoff ist, und
• R₂₀ Wasserstoff oder C₁-C₄ Alkyl ist r,m,A,R₁₂,R₁₃ und R₁₄ oben angegebene Bedeutung haben.

Particularly preferred compounds of the formula XVI are those in which

• M is Ca ²⁺ , Zn ²⁺ or Ni ²⁺ , and
• q is 2, and
• L is a t-toothed group of the formula IVc which is substituted by at least one group of the formula VI, and
• t is 2, where
• R _{15 and} R _{16 are} hydrogen, and
• R _{18 is} a group -N (R ₂₅ ) R ₂₇ , wherein
• R _{25 is} hydrogen, C ₁ -C ₁₂ alkyl or a group -CH ₂ -CH (R ₅ ) -OH, in which R _{5 is} hydrogen or methyl, and
• R _{27 is} hydrogen, or a C ₁ -C ₄ alkyl substituted by a group of the formula Vc or a group of the formula VI, where
• ^X _{2 is} -0-, and
• Y represents hydrogen, methyl or acetyl, and
• R _{21 is} hydrogen or methyl, and
• ^R 23 is a group of formula VI, and
• _{R19 is} hydrogen, and
• R _{20 is} hydrogen or C ₁ -C ₄ alkyl is r, m, A, R ₁₂ , R ₁₃ and R ₁₄ have the meaning given above.

• M Ca²⁺, Zn²⁺ oder Ni²⁺ ist, und
• q 2 ist, und
• L eine t-zähnige Gruppe der Formel IVe, welche mindestens mit einer Gruppe der Formeln Va oder VI substituiert ist, bedeutet, und
• t 2 ist, und
• R₁₈undR₁₉ zusamamen =O sind, und
• R₁₅ Wasserstoff, C₁-C₄ Alkyl, welches gegebenenfalls mit einer Gruppe der Formeln Va oder VI substituiert ist oder eine Gruppe Vc oder einen Rest -OR₂₄ bedeutet, und
• R₁₆ Wasserstoff ist, wobei
• X₁ -NR₂₅ bedeutet, und
• R₂₁ Wasserstoff oder Methyl ist, und
• Y Wasserstoff, Methyl oder Acetyl ist, und
• R₂₄ mit-einer Gruppe der Formel Vc substituiertes C₁-C₄ Alkyl bedeutet, wobei
• R₂₃ eine Gruppe der Formel VI und
• X₂ -O- bedeutet, und
• R₁₆ Wasserstoff ist, und
• R₂₀ Wasserstoff, C₁-C₅ Alkyl, mit einer Gruppe der Formel Vc substituiertes C₁-C₄ Alkyl oder C₂ Alkenyl oder eine Gruppe der Formel Va, worin X₂, R₂₁ und .Y die angegebene Bedeutung haben, und
• R₂₅ Wasserstoff, C₁-C₁₂ Alkyl oder eine Gruppe -CH₂-CH(R₅)-OH, worin R₅ Wasserstoff oder Methyl ist, bedeutet, und
• r.,m,A,R₁₂,R₁₃ und R₁₄ oben angegebene Bedeutung haben.

Particularly preferred compounds of the formula XVI are also those in which

• M is Ca ²⁺ , Zn ²⁺ or Ni ²⁺ , and
• q is 2, and
• L is a t-toothed group of the formula IVe which is substituted by at least one group of the formulas Va or VI, and
• t is 2, and
• R _{18 and} R ₁₉ together = O, and
• R _{15 is} hydrogen, C ₁ -C ₄ alkyl, which is optionally substituted by a group of the formulas Va or VI or a group Vc or a radical -OR ₂₄ , and
• R _{16 is} hydrogen, wherein
• X ₁ denotes -NR ₂₅ , and
• R _{21 is} hydrogen or methyl, and
• Y is hydrogen, methyl or acetyl, and
• R ₂₄ means C ₁ -C ₄ alkyl substituted with a group of the formula Vc, where
• R _{23 is} a group of the formula VI and
• X ₂ denotes -O-, and
• R _{16 is} hydrogen, and
• R _{20 is} hydrogen, C ₁ -C ₅ alkyl, C ₁ -C ₄ alkyl or C ₂ alkenyl which is substituted by a group of the formula Vc or a group of the formula Va, where X ₂ , R ₂₁ and .Y have the meaning indicated, and
• R _{25 is} hydrogen, C ₁ -C ₁₂ alkyl or a group -CH ₂ -CH (R ₅ ) -OH, in which R _{5 is} hydrogen or methyl, and
• r., m, A, R ₁₂ , R ₁₃ and R ₁₄ have the meaning given above.

• M Ca²⁺, Zn²⁺ oder Ni²⁺ ist, und
• q 2 ist, und
• L eine t-zähnige Gruppe der Formel IVc, welche mindestens mit einer Gruppe der Formel Va oder VI substituiert ist, bedeutet, und
• t 2 ist, und
• R₁₈undR₁₉ zusammen =NR₂₇ sind, und
• R₁₅ Wasserstoff, C₁-C₄ Alkyl, welches gegebenenfalls mit einer Gruppe der Formeln Va oder VI substituiert ist oder eine Gruppe Vc, oder einen Rest -OR₂₄ bedeutet, und
• R₁₆ Wasserstoff ist, wobei
• X₁ -N-R₂₅ bedeutet, und
• R₂₁ Wasserstoff oder Methyl ist, und
• Y Wasserstoff, Methyl oder Acetyl ist, und
• R₂₄ mit einer Gruppe der Formel Vc substituiertes C₁-C₄ Alkyl bedeutet, wobei
• R₂₃ eine Gruppe der Farmel VI, und
• X₂ -O- bedeutet, und
• R₂₀ Wasserstoff, C₁-C₅ Alkyl oder mit einer Gruppe der
• Formel Vc substituiertes-C₁-C₄ Alkyl ist, und R₂₅ Wasserstoff, C₁-C₁₂ Alkyl oder eine Gruppe -CH₂-CH(R₅)-OH, worin R₅ Wasserstoff oder Methyl ist, und
• R₂₇ eine Gruppe der Formel VI bedeutet, und r, _m, _A, R₁₂, _R13 und _R14 oben angegebene Bedeutung haben.

Particularly preferred compounds of the formula XVI are also those in which

• M is Ca ²⁺ , Zn ²⁺ or Ni ²⁺ , and
• q is 2, and
• L is a t-toothed group of the formula IVc which is substituted by at least one group of the formula Va or VI, and
• t is 2, and
• R _{18 and} R ₁₉ together = NR ₂₇ , and
• R _{15 is} hydrogen, C ₁ -C ₄ alkyl, which is optionally substituted by a group of the formulas Va or VI or a group Vc, or a radical -OR ₂₄ , and
• R _{16 is} hydrogen, wherein
• X ₁ denotes -NR ₂₅ , and
• R _{21 is} hydrogen or methyl, and
• Y is hydrogen, methyl or acetyl, and
• R _{24 is} C ₁ -C ₄ alkyl substituted by a group of the formula Vc, where
• R _{23 is} a group of Farmel VI, and
• X ₂ denotes -O-, and
• R _{20 is} hydrogen, C ₁ -C ₅ alkyl or with a group of
• Formula Vc is substituted -C ₁ -C ₄ alkyl, and R _{25 is} hydrogen, C ₁ -C ₁₂ alkyl or a group -CH ₂ -CH (R ₅ ) -OH, wherein R _{5 is} hydrogen or methyl, and
• R ₂₇ denotes a group of the formula VI, and r, _m , _A , R ₁₂ , _R13 and _R14 have the meaning given above.

• Der Ni²⁺-1:2-Komplex des N-Methyl-N-(2-hydroxyphenyl)-N-[1',2',2',6',6'-pentamethyl-piperidin-4'-oxy-carbonylmethyl]-azomethins (4-Amino-2,2,6,6-tetramethyl-piperidin)₂.

Examples of compounds of the formula XVI are:

• The Ni ²⁺ -1: 2 complex of N-methyl-N- (2-hydroxyphenyl) -N- [1 ', 2', 2 ', 6', 6'-pentamethyl-piperidine-4'-oxy- carbonylmethyl] -azomethine (4-amino-2,2,6,6-tetramethyl-piperidine) ₂ .

The Al ³⁺ -1: 3 complex of N-phenyl-N- (2-hydroxyphenyl) -N- [2 '- (1-benzyl-2,2,6,6-tetramethyl-piperidine-4-oxy- carbonyl) phenyl] azomethine.

The Ni ²⁺ -1: 1 complex of hexamethylene-di- {N-methyl- [2-hydroxy-5- (1 '-, 2', 2 ', 6', 6'-pentamethyl-piperidin-4 ' -yl)] - azomethins (triethanolamine) ₂ .

The Ca ²⁺ -1: 2 complex of N- (1,2,2,6,6-pentamethyl-piperidin-4-yl) -Nn-butyl-N - ([2'-hydroxy-5'-t octyl] benzyl) amines (dibenzylpropylamine) ₂ .

The Ni ²⁺ -1: 2 complex of hexamethylene-di- {N- [2-hydroxy-4- (1'-hexyl-2 ', 2', 6 ', 6'-tetramethyl-piperidine-4'- oxy-carbonyl-methyl-oxy)] - benzyl-amine · (triethanolamine) ₂ .

The Mg ²⁺ -1: 2 complex of 2- {1 ', 2', 2 ', 6', 6'-pentamethylpiperidine-4-oxycarbonyl} -4- {1 ', 2', 2 ', 6' , 6'-pentamethylpiperidine-4-oxycarbonyl-methyl-oxy} phenol · (4-dimethylamine-2,2,6,6-tetramethyl-piperidine) ₂ .

The Ni ²⁺ -1: 2 complex of 2-methyl-carbonyl {-3,5-di- 2 ', 2', 6 ', 6'-tetramethyl-piperidine-4-oxycarbonyl-methyloxy} - phenol Triethanolamine) ₂ .

The preparation of the compounds of the formula I is known.

The compounds of the formula I in which s and m are 0 are most easily obtained by mixing about one mole of the free ligand [L] H _r with about r / ^* moles of an alkali metal or alkaline earth metal hydroxide, alcoholate, hydride or -Amids or also r / _2q * moles of an alkali or alkaline earth carbonate in an inert, organic solvent. The reaction can take place at room temperature or to accelerate the reaction at elevated temperatures up to the reflux temperature. The easiest way to work is at room temperature. Particularly suitable alkali metals are lithium, sodium, potassium or rubidium, especially sodium or potassium. Calcium is particularly suitable as an alkaline earth metal. q ^* defines the charge of the alkali or alkaline earth metal cation M * used. Alcohols such as methanol or ethanol, ethers such as dioxane, tetrahydrofuran or diethyl ether are suitable as inert organic solvents; aromatic hydrocarbons such as benzene, taluol, xylene; aliphatic hydrocarbons such as hexane or ligroin; or amides such as dimethylformamide or hexamethylphosphoric triamide.

können anschliessend auf einfache Weise mit einem Metallsalz ML*_q umgesetzt werden. Es gelangen dabei vor allen q/_r Mole der Verbindung [L]M*_r/q* pro Mol ML^* in einem inerten organischen Lösungsmittel zum Einsatz. Als Lösungsmittel eignen sich die oben beschriebenen. Die Temperatur kann wiederum von Raumtemperatur bis zur Rückflusstemperatur gewählt werden. Als Anion L^* eignen sich insbesondere Halogenic vor allem Chlorid, oder Carboxylatanionen, wie Acetat oder Capronat.The alkali or alkaline earth salts obtained in this way

can then be easily implemented with a metal salt ML * _q . All q / _r moles of the compound [L] M * _{r / q *} per mole of ML ^{* are used} in an inert organic solvent. The solvents described above are suitable as solvents. The temperature can in turn be selected from room temperature to the reflux temperature. Particularly suitable as anion L ^* are halogenic, especially chloride, or carboxylate anions, such as acetate or capronate.

It is also possible to combine the two process steps described above or to use hydrates of the compounds described.

Is used as ML * q e.g. If a hydroxide or carbonate is used, the alkali or alkaline earth metal salt formation can even be dispensed with.

If s is not 0, the procedure is in principle as described, wherein ^(qs) / r moles of a compound [L] M * _{r / q} and s moles of a compound BM ^* are reacted with a metal salt of the formula ML ^*. The same result is obtained by ligand exchange reactions, for example using MB _q with ^(qs) / r moles [L] M * _{r / q} . The compounds B are known and can be prepared by known methods.

If the compound of the formula I is to contain an amine A, the simplest solution is to use a solution of the compound [M ^{q +} ] [L ^r- ] _{(qs) / r} · [B ^- ] _s in one of the described processes aprotic inert solvent heated in the presence of at least m moles of compound A. The temperature can be up to the reflux temperature, but should in any case be at least 30 ° C. Advantageous results are achieved by refluxing, using a water separator.

The amines A are known and can be prepared by known methods. Some such compounds are described, for example, in U.S. Pat. 3,901,031 or if A contains piperidyl residues also described in DT-OS 2,349,962.

The condition that a chelating ligand according to The present invention must meet that it contains at least one group of formula IIa or IIb. How to obtain compounds which contain groups IIa or IIb has been described in the literature. For example, derivatives of pyrrolidine in DT-OS 2,459,331; of the Imidazoli. dins in DT-OS 2,427,853 or DT-OS 2,500,313; 1,4-diazacycloheptanone in DT-OS 2,428,877 or DT-OS 2,621,924; piperazine in DT-OS 2,315,042; 1-aza-4-thiacyclohexane in DT-OS 1,351,865; dipiperidyl in DT-OS 2,425,984 and piperidine, for example in DT-OS 2,258,752, 2,040,975; 2,227,689, U.S. Pat. No. 3,639,409, 3,640,928 or GB-Pat.No. 1,262,234.

• Handelt es sich um eine Gruppe der Formel Va oder VI,so kann von den entsprechenden 4-Hydroxypiperidinen (bekannt aus der DT-OS 2,352,658) oder den 4-Aminopiperidinen (bekannt aus dem US-Pat. 3,684,765) ausgegangen werden. Die 4-OH-Verbindungen können allgemein aus den 4-Oxopiperidinen der Formel XVII
  
  in der R₂₁ und Y die oben angegebene Bedeutung haben, durch Reduktion, z.B. katalytische Hydrierung über Raney-Nickel hergestellt werden, während die 4-NH₂-Verbindungen z.B. mittels reduktiver Umsetzung mit Ammoniak aus einer Verbindung der Formel XVII erhältlich sind.

As already mentioned, those chelating agents which contain one or more piperidine residues are of particular interest. This is also expressed in that the particularly preferred compounds contain groups of the formula Va, Vb or VI, which can be obtained, for example, as follows:

• If it is a group of the formula Va or VI, the corresponding 4-hydroxypiperidines (known from DT-OS 2,352,658) or the 4-aminopiperidines (known from US Pat. No. 3,684,765) can be used. The 4-OH compounds can generally be derived from the 4-oxopiperidines of the formula XVII
  
  in which R ₂₁ and Y have the meaning given above, are prepared by reduction, for example catalytic hydrogenation over Raney nickel, while the 4-NH ₂ compounds are obtainable, for example, by means of reductive reaction with ammonia from a compound of the formula XVII.

The 4-oxopiperidines of the formula XVII, in which Y is hydrogen, can be prepared by various processes.

For example, by W. Traube in Chem. Ber. 41, 777 (1908) describes the reaction of an aliphatic ketone with ammonia.

4-Oxopiperidines of the formula XVII, in which Y is hydrogen, can also be analogous to that in US Pat. 3,513,170 described methods are prepared. Here, an alkyl-substituted tetrahydropyrimidine is hydrolytically rearranged in the presence of an acid catalyst.

NH compounds of the formula XVII which have different substituents in the 2- and 6-positions can be prepared by reacting a ketone of the formula CH ₃ -CO-CH ₂ R ₂₁ with ammonia. The pyrimidine formed is, as in Helv. Chim. Acta 30, 14 (1947), hydrolyzed to an amino ketone of the formula XVIII.

The compounds of the formula XVIII are reacted in a second process step with ammonia and a ketone CH ₃ -CO-CH ₂ -R ₂₁ , as described, for example, in 'Monthly. Chemie 88, 464 (1957). The compounds of formula XVII, in which Y is hydrogen, can be obtained from the pyrimidine thus obtained by hydrolysis.

Compounds of the formula XVII, in which Y is not hydrogen, or also those which correspond to the protonated form of the group of the formula Vb, can be prepared by substitution from the corresponding NH compounds. These are the usual substitution reactions for secondary amines, although these are slower due to the steric hindrance caused by the methyl group or the group -CH2-R21. The _N - _H compounds can be reacted, for example, with alkyl, alkenyl, aralkyl or alkoxyalkyl halides, with dialkyl sulfates, with epichlorohydrins, with esters of chlorocarboxylic acids such as chloroacetic acid esters or acid chlorides or anhydrides.

und anschliessender Acylierung mit einem Acylchlorid der Formel R₈Cl eingeführt werden. Analog kann ein Hydroxyalkyl-Rest eingeführt werden.The group -CH ₂ -CH (R ₇ ) -OR ₈ can by reacting the NH-piperidines with an epoxide of the formula

and subsequent acylation with an acyl chloride of the formula R ₈ Cl are introduced. Analogously, a hydroxyalkyl radical can be introduced.

Compounds of the 2,2,6,6-tetramethyl-4- (alkoxycarbonylcyanomethyl) piperidine type which can be used as intermediates are also known from British Patent 1,214,426.

The introduction of a radical R ₂₂ is based on the 4-hydroxy. Or. 4-aminopiperidines by customary methods, for example by reaction with a chloride of the formula R ₂₆ Cl, or hydrogenolytic condensation with H ₂ NR ₂₆ -

The requirement which is placed on the groups of the formula IIa, IIb, Va, Vb and VI described at the points indicated is that they contain a functional group, in particular an amino, hydroxy or carboxylic acid (ester) group, which enables the groups mentioned to be incorporated into the chelating molecule by means of customary transesterification or condensation reactions.

If these groups are, for example, in the substituents R ₁₅ or R ₁₆ as alkyl substituted by a group Va or Vb, in which Z is -O-, a hydroxyphenylalkyl chloride with an alcohol derived from the groups Va or Vb, or amine, is known in a known manner implemented in the presence of a base. The reaction with an alcoholate, which is known under the name Williamson synthesis, is equally suitable. If in the formula Vb Z is -OC (O) - or R ₁₅ or R _{16 is} a group of the formula Vc, in which R _{23 is,} for example, a radical VI, the easiest way of introducing them is by using a common transesterification reaction to aromatic carbon - .. acids, such as benzoic acid, phenylacetic acid or β-phenyl-propionic acid, with an alcohol derived from the formula Va or Vb. This reaction can be acid or base catalyzed. If R ₁₅ or R _{16 is} an alkoxy group which is substituted by a radical of the formula Vc, their on occurs leadership, for example, by the reaction of a phenol, such as a catechol, resorcinol, hydroquinone, pyrogallol, or phloroglucin with a haloalkyl derivative of the group of the formula Vc in an inert solvent in the presence of a base. If R ₁₅ or R _{16 is a} group of the formula VI, a phenol is reacted with a 4-oxo derivative of a group of the formula VI in the presence of an acid and subsequent reduction, as described, for example, in US Pat. 3,847,930.

If L is a group of the formula IVa, its preparation can be carried out analogously to the description in US Pat. 2,971,941 take place, about 2 moles of a phenol being reacted with 1 mole of SCl ₂ and the introduction of the radicals R ₁₅ and R ₁₆ as described above takes place before or after the SCl ₂ stage. If R _{15 is} a group of the formula VI, this is introduced before the SCl ₂ stage. The chelating agents H ₂ L corresponding to formula IVa thus prepared are new and therefore form an object of the present invention. Compounds which contain a group of the formula IVa are distinguished by the fact that r can have a value of 1 or 2. This depends on the ratio of the onset concentration of the free ligand and the metal salt in the chelation step described above.

If L is a group of the formula IVb, its preparation can be carried out analogously to the compounds from GB Pat. 878,362 or GB Pat. 1,332,560. If R ₁₅ or R ₁₆ contain a group IIa or IIb, or Va, Vb or VI, these are introduced as described above. If R _{17 is} a group of the formula Vc in which R _{23 is} a radical of the formula VI, the known compounds are used in which R ₂₃ means alkyl, and esterifies it with an alcohol derived from group Va in a known manner. If R _{17 is} a group of the formula -OR ₂₄ , the simplest way to react the analogue compound in which R _{17 is} hydroxy with a compound CLR ₂₄ . Some of the chelating agents of formula IVb are known from JA-OS 51-88484.

If L is a group of the formula IVc, if R ₁₅ or R ₁₆ contain a group IIa or IIb or Va, Vb or VI, these are introduced as described above.

If R ₁₈ and R ₁₉ together = 0, salicylic acid or its alkyl ester, salicylamide or an a-hydroxyphenyl ketone are generally used as starting materials. The introduction of a group of the formula Va as R ₂₀ is therefore carried out by a simple transesterification reaction starting from a salicylic acid ester with an alcohol or amine, which is derived from the formula Va. In an analogous manner, compounds can be prepared by transesterification in which R ₂₀ denotes an alkyl, alkenyl, cycloalkyl or aryl group substituted by a group of the formula Vc. In order to arrive at the compounds in which R _{20 represents} a group of formula VII, approximately 2 moles of a salicylic acid ester are reacted with approximately 1 mole of a diol. Before or after this stage, the desired R ₁₅ and R ₁₆ radicals can be incorporated in the manner indicated above. The chelating agents of the formula IVc thus obtained, in which R ₁₈ and R ₁₉ together are = O, are new compounds and therefore form an object of the present invention.

Known compounds can be obtained from the keto compounds thus obtained The chelating agents of the formula IVc, in which R ₁₈ and R ₁₉ together = NR ₂₇ mean, are prepared. The keto compounds are reacted with a primary amine in a common condensation reaction. This can be an amine which is derived from a group of the formula Va, in which X _{1 is} -NH, or it can also be an alkyl, alkenyl, cycloalkyl or arylamine which is substituted by a group of the formula Vc . The compounds of the formula IVc obtained in which R ₁₈ and R ₁₉ together = NR ₂₇ are new substances and therefore also form an object of the present invention. The compounds in which R _{27 is} a group of the formula VIIIb are obtained by replacing the primary amine with a diamine and reacting with 2 moles of the keto compound.

The described azomethine compounds of the formula IVc can be reduced to the compounds of the formula IVc by known reduction methods, for example by means of hydrogen to Pd / C, in which X ₁ denotes -NH. Another variant is to use a secondary amine HN (R ₂₅ ) R ₂₇ in a Mannich reaction in the presence of an aldehyde, preferably formaldehyde. If the chelating agent contains a group of the formula VIIIa as R ₂₇ , the preparation is carried out by reducing the corresponding di-azomethine compound. The compounds of the formula IVc obtained in the manner described, in which R ₁₈ denotes -N (R ₂₅ ) R ₂₇ , are new and therefore also constitute an object of the invention.

If ligands are used which have an r = 2, oligomers or even polymers can be formed. These are characterized by the fact that they contain several centers capable of chelation and therefore have the possibility tie multiple metal cents. Such higher molecular substances are characterized by an increased resistance to extraction. Such higher molecular weight substances are new and are therefore also an object of the invention, which is expressed above all by the fact that the ratio of metal to ligand L given in formula I is also correct in this case if it is based on the building block on which the polymer is based becomes. The molecular weight is approximately 400-10000, preferably 400-2000.

According to the present invention, the compounds of the formula I can be used as stabilizers for plastics against their damage by the action of oxygen, heat and light. Examples of such plastics are the polymers listed in DT-OS 2,456,864 on pages 12-14.

Of particular importance is the stabilization of polyolefins, styrene polymers and polyurethanes, for which the compounds of the formula I are outstandingly suitable. Examples include high and low density polyethylene, polypropylene, ethylene-propylene copolymers, polystyrene, styrene-butadiene-acrylonitrile copolymers, mixtures of polyolefins or of styrene polymers, polyurethanes based on polyether or polyester in the form of films, fibers, lacquers, elastomers or foams.

The stabilizers are added to the plastics in a concentration of 0.01 to 5% by weight, calculated on the material to be stabilized. Preferably 0.03 to 1.5, particularly preferably 0.2 to 0.6% by weight of the compounds, calculated on the material to be stabilized, are incorporated therein.

The incorporation can take place after the polymerization, for example by mixing the compounds and, if appropriate, further additives into the melt according to the methods customary in industry, before or during shaping, or also by applying the dissolved or dispersed compounds to the polymer, optionally with subsequent addition Evaporation of the solvent.

The new compounds can also be added to the plastics to be stabilized in the form of a masterbatch which contains these compounds, for example in a concentration of 2.5 to 25% by weight.

In the case of cross-linked polyethylene, the compounds are added before cross-linking.

The invention therefore also relates to the plastics stabilized by the addition of 0.01 to 5% by weight of a compound of the formula I, which may also contain other known and customary additives. The plastics stabilized in this way can be used in various forms, e.g. as foils, fibers, tapes, profiles or as binders for paints, adhesives or putties.

• Antioxydantien, wie einfache 2,6-Dialkylphenole, Derivate von alkylierten Hydrochinonen, hydroxylierte Thiodiphenyl- äther, Alkyliden-bisphenole, 0-, N- und S-Benzylverbihdungen, hydroxybenzylierte Malonester, Hydroxybenzyl-Aromaten, s-Triazinverbindungen, Amide der β-(3,5-Di-tert.-butyl-4-hydroxyphenyl)-propionsäure, Ester der β-(3,5-Di-tert.-butyl-4-hydroxyphenyl)-propionsäure, Ester der β-(5-tert.-Butyl-4-hydroxy-3-methylphenyl)-propionsäure, Ester der 3,5-Di-tert.-butyl-4-hydroxyphenylessigsäure, Acylaminophenole, Benzylphosphonate, Aminoarylderivate, UV-Absorber und Lichtschutzmittel, wie 2-(2'-Hydroxyphenyl)-benztriazole, 2,4-Bis-(2'-hydroxyphenyl)-6-alkyl-s-triazine, 2-Hydroxybenzophenone, 1,3-Bis-(2'-hydroxybenzoyl)-benzole, Ester von gegebenenfalls substituierten Benzoesäuren, Acrylate; des weiteren Nickelverbindungen, sterisch gehinderte Amine, Oxalsäurediamide, Metalldesaktivatoren, Phosphite, Peroxidzerstörende Verbindungen, Polyamidstabilisatoren, basische Co-Stabilisatoren, PVC-Stabilisatoren, Nukleierungsmittel oder sonstige Zusätze wie z.B. Weichmacher, Gleitmittel, Emulgatoren, Füllstoffe, Russ, Asbest, Kaolin, Talk, Glasfasern, Pigmente, optische Aufheller, Flammschutzmittel, Antistatica.

Examples of further additives with which the stabilizers which can be used according to the invention can be used are:

• Antioxidants, such as simple 2,6-dialkylphenols, derivatives of alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylidene bisphenols, 0-, N- and S-benzyl compounds, hydroxybenzylated malonic esters, hydroxybenzyl aromatics, s- Triazine compounds, amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid, esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid, acylaminophenols, benzylphosphonates, aminoaryl derivatives, UV absorbers and light stabilizers, such as 2- (2'-hydroxyphenyl) benzotriazoles, 2,4-bis (2'-hydroxyphenyl) -6-alkyl-s-triazines, 2-hydroxybenzophenones, 1,3-bis (2'-hydroxybenzoyl) - benzenes, esters of optionally substituted benzoic acids, acrylates; furthermore nickel compounds, sterically hindered amines, oxalic acid diamides, metal deactivators, phosphites, peroxide-destroying compounds, polyamide stabilizers, basic co-stabilizers, PVC stabilizers, nucleating agents or other additives such as plasticizers, lubricants, emulsifiers, fillers, carbon black, asbestos, kaolin, talc, Glass fibers, pigments, optical brighteners, flame retardants, antistatic agents.

Examples of further additives with which the stabilizers which can be used according to the invention can be used can be found in DT-OS 2,427,853 on pages 18-24.

The preparation and use of the compounds according to the invention is described in more detail in the following examples.

example 1

137.2 g (0.5 mol) of N- [2-hydroxybenzyl] -N-methyl-N- [2,2,5,6-tetramethyl-piperidyl-4] -amine were dissolved in 200 ml of ethanol, and at A solution of 11.5 g of Na in 300 ml of ethanol was added dropwise at room temperature over 1.5 hours and the mixture was stirred at 50 ° C. for a further 1.5 hours. 59.4 g of NiCl ₂ · 2H ₂ 0 dissolved in 300 ml of ethanol was added dropwise over 2 hours and then maintaining the solution for 2 hours at reflux. The solvent was evaporated, the residue was taken up in hot hexane and the NaCl was filtered off. After the hexane solution had cooled, the stabilizer 1 crystallized out as a green-yellow colored compound.

The following compounds were prepared analogously to compound I.

Example 7

zeigte folgende Analyse:

15.66 g of di- {2-hydroxy-5-t-octyl-3- [N-methyl-N- (2,2,6,6-tetramethylpiperidyl-4) aminomethyl] phenyl} sulfide was added in 100 ml Dissolved ethanol and 1.36 g of sodium ethanolate were added under a nitrogen atmosphere. The reaction mixture was stirred for 20 minutes at room temperature and then 1.65 g of NiCl ₂ .2H ₂ O dissolved in 40 ml of ethanol was added dropwise. The mixture was stirred at 24 ° C for 12 hours. The precipitated NaCl was filtered off and the solvent was evaporated. The 16.9 g of pale green stabilizer 7 thus obtained

showed the following analysis:

Example 8

zeigte folgende Analyse:

12.6 g [0.02 mol] of the Ni salt of N-methyl-N- [2,2,6,6-tetramethyl-piperidyl-4) amine and 4 g (0.02 mol) of N, N-Dimethyl-N- [1,2,2,6,6-pentamethylpiperidyl-4] amines were dissolved in 200 ml of toluene and refluxed for 7 hours over the water separator. The solvent was then evaporated off, the residue was taken up in hot hexane and, after cooling, the crystals formed were filtered off with suction and dried in a vacuum oven at 60 ° C. for 20 hours. The product_

showed the following analysis:

The following connection types were produced analogously to stabilizer 8:

The corresponding ligands A used as amines are summarized in the examples in the table below.

The following compounds were prepared analogously to the stabilizer according to Example ₈ :

The following compounds were prepared analogously to the stabilizer according to Example 8:

Example 19

a) 22.1 g of 3,3'-di- (t-octyl) -6,6'-diphenyl sulfide and 26.8 g of 4-n-octylamino-2,2,6,6-tetramethylpiperidine were in 100 ml of ethanol dissolved. 8.6 g of a 35% solution of formaldehyde were added dropwise at 23 ° C. under nitrogen. The reaction mixture was kept at reflux temperature for 4 h and the solvent was then evaporated off under vacuum, which gave 35.2 g of the di- {2-hydroxy-5-t.octyl-3- [N-octyl-N- (2.2, 6,6-tetramethylpiperidyl-4) aminomethyl] phenyl} sulfide.

welcher folgende Analysenwerte aufwies:

b) 20.08 g of the product from Example 19a was treated analogously to Example 5 with sodium ethanolate (from 0.92 g of Na in 20 ml of ethanol) and 3.3 g of NiCl ₂ .2H ₂ O. The product thus obtained: 21.3 g of stabilizer 19

which had the following analytical values:

Example 20

welche folgende Analysenwerte besassen:

13.3 g of stabilizer 19 were taken up in 150 ml of ethanol, and 1.87 g of 4-amino-2,2,6,6-tetramethylpiperidine in 20 ml of ethanol were added dropwise under a nitrogen atmosphere at 24 ° C., and the reaction solution was added during 16 h stirred. The solvent was then evaporated to give 15.0 g of green crystals (stabilizer 20).

which had the following analytical values:

Example 21

19.7 g (N- [2-Hydroxy-4-t.octylbenzyl] -N-methyl-N- [2,2,6,6-tetramethyl-piperidinyl-4] amine in 150 ml methanol were mixed with freshly prepared Sodium methylate (from 1.15 g of Na and 40 ml of methanol) After stirring for 1/2 hour, 4.3 g of NiCl ₂ .2H ₂ O in 50 ml of methanol were added dropwise and stirring was continued for 5 hours at 24 ° C. The sodium was filtered off and the solvent was evaporated off, the green-brown residue

Stabilizer 21 has the following analysis data:

Example 22

52.5 g (0.1 mol) of N- [2-hydroxybenzyl] -N- [2,2,6,6-tetramethylpiperidyl-4] amine were dissolved in 250 ml of methanol and mixed with 100 ml of a 1 molar sodium methylate solution . 25 ml of a 2 molar solution of anhydrous nickel chloride in methanol (corresponding to 0.05 mol of NiCl ₂ ) were added to this solution within 1/2 hour at room temperature. added dropwise and the reaction mixture boiled under reflux for 30 minutes. The separated sodium chloride was filtered off and the filtrate was evaporated to dryness. The residue was extracted with ether at room temperature, the extract was evaporated and dried at 80 ° under a pressure of 11 mm Hg. A dark beige powder of the composition was obtained:

Example 23

52.5 g (0.1 mol) of N- [2-hydroxybenzyl] -N- [2,2,6,6-tetramethylpiperidyl-4] amine were dissolved in 250 ml of absolute ethanol and with 100 ml of a 1 molar sodium methylate solution transferred. A solution of 6.81 g of 0.05 mol) of anhydrous zinc chloride in 20 ml of absolute ethanol was added dropwise to this solution, the mixture was heated under reflux for 1 1/2 hours and the solvent was then evaporated off. The residue was then extracted with hot toluene, the extract evaporated and dried at 60 ° under a pressure of 11 μm Hg. A yellowish powder of the following composition was obtained:

Example 24 Sun protection effect in high pressure polyethylene foils

100 parts of low-density polyethylene granules (= 0.917) are homogenized with 0.05 part of a stabilizer from the following table in a Brabender plastograph at 180 ° C. for 10 minutes. The mass obtained in this way is removed from the kneader as quickly as possible and pressed to a 2 - 3 mm thick plate in a toggle press. Part of the raw compact obtained is cut out and pressed between two high-gloss hard aluminum foils with a hand-hydraulic laboratory press for 6 minutes at 170 ° and 12 tons pressure to a 0.1 mm thick foil, which is immediately quenched in cold water. Sections of 60 x 44 mm are now punched out of this and exposed in the Yenotest 1200. These test specimens are removed from the exposure apparatus at regular intervals and checked for their carbonyl content in an IR spectrophotometer. The increase in carbonyl absorbance during exposure is a measure of the photooxidative degradation of the polymer (sLBlaban et al., J. Polymer Sci. Part C, 22,

1059-1071 (1969); J.F. Hecock, J.Polymer Sci. Part A-1, 22, 2921-34 (1969); D.J. Carlsson and DM. Wiles, Macromolecules 2, 587-606 (1969) and experience has shown that the mechanical properties of the polymer decrease.

The measure of the protective effect is the time until a carbonyl extinction of 0.100 is reached.

The results are summarized in Table I.

Example 25

100 parts of polypropylene powder (melt index 1.5 g / 10 min., 230 ° C., 2160 g load) were mixed in a drum mixer with 0.1 part of pentaerythritol tetrakis [3- (3'5'-di-tertiary-butyl-4-hydroxyphenyl ) propionate] and 0.15 parts of the stabilizers listed in the table below. mixes and extruded and granulated in an extruder at 200 - 220 ° C. The obtained granulate was conventionally se processed into films by means of an extruder having wide-slot _U, which were cut into strips, which were then stretched to six times their length at elevated temperature. The titer of these tapes is 700 - 900 den, their width 4 mm, their tensile strength 5.5 - 6.5 g / den.

These ribbons were exposed in a Xenotest 1200. Samples were subjected to a tensile strain test at regular intervals, with a progressive decrease in the tensile strength with increasing exposure. The exposure time until the tear strength drops to half the initial value is extended by the action of the light stabilizers.

Example 26 Sun protection effect in PP fibers (130/37)

1000 parts of unstabilized polypropylene powder (melt index ~ 18) are mixed in a drum mixer with 1 part of pentaerythrytyl tetrakis [3- (3,5-di-tert-butyl-4-hydroxylphenyl) propionate] and with 3 parts of the in the table listed light protection agent mixed and then extruded in an extruder at 220 ° C and granulated. The granules obtained are spun into a 130/37 denier multifilament in a laboratory melt spinning plant at a maximum temperature of 270 ° C. and a speed of 300 m / minute. This is drawn and twisted using a draw twisting machine. The draw ratio is 1: 5.6 and the thread count is 15 / meter, so that multifilaments 130/37 denier are finally obtained. These multifilaments are mounted on white cardboard and exposed in the Xenotest 1200.

The exposure time up to 50% loss of tensile strength is the measure of the protective effect.

The results are summarized in the table:

Claims (9)

1. New metal complexes of the general formula I

wherein M is a double or triple positively charged metal ion, q is 2 or 3, and L is a t-dentate chelating anion containing 1 or 2 phenolate groups, which has at least one group of the formulas IIa or IIb

contains what t is 2, 3 or 4, and R ₁ , R ₂ , R ₃ and R _{4 are} independently alkyl, or R ₁ and R ₃ together are alkylene, or R ₁ and R ₂ or R ₃ and R _4, independently of one another, are alkylene or azaalklene, and R _{5 is} hydrogen, methyl or phenyl, and Y is hydrogen, oxyl, alkyl, alkenyl, alkynyl, alkoxyalkyl, aralkyl, 2,3-epoxypropyl, an aliphatic acyl group or one of the groups -CH ₂ COOR ₆ , -CH ₂ -CH (R ₇ ) -OR ₈ , -COOR ₉ or -CONHR ₉ , wherein R _{6 is} alkyl, alkenyl, phenyl, aralkyl or cycloalkyl and R _{7 is} hydrogen, methyl or phenyl, and R ₈ denotes hydrogen, an aliphatic or aromatic, an araliphatic or alicyclic acyl group ', in which the aromatic part can optionally be substituted by chlorine, alkyl, alkoxy and / or hydroxy, and R ₉ denotes alkyl, cyclohexyl, phenyl or benzyl, and R _{10 is} a trivalent and R _{11 is} a divalent organic radical, where R ₁₀ and R _{11 complete} the N-containing ring to form a 5-, 6- or 7-membered ring, and r is the number of coordinatively bound phenolate anions in molecule 1 or 2, and B is a single negatively charged ligand, and s is an integer from 0 to 2, where the sum must be (qs) / r ± s = q, and m is an integer from 0 to 3, the sum t. [(qs) / r] + s + m being the coordination number of the metal ion M, where AH ₂ 0 or an amine of formula III

is what R _{12 is} optionally substituted alkyl, cycloalkyl, aryl, aralkyl, an optionally substituted aminoalkyl group or a piperidinyl group, and R _{13 represents} hydrogen or optionally substituted alkyl, cycloalkyl, an optionally substituted aminoalkyl group or a piperidinyl group, or R ₁₂ and R ₁₃ together with the N atom represent an alkyl group-substituted or unsubstituted pyrrolidine,. Form piperidine or morpholine ring, and R _{14 represents} hydrogen or optionally substituted alkyl. 2. New metal complexes according to claim 1 of the formula I in which L ^{r is} a 2-, 3- or 4-toothed chelating agent selected from the class consisting of groups IVa, IVb and IVc

is what u is 0, 1 or 2, and r has the meaning given above, and R _{15 and} R ₁₆ independently of one another are hydrogen, C ₁ -C ₁₈ alkyl, which may optionally contain a group Va, Vb or Vc:

can be substituted; or a group Vc, or a p-group of formula VI

Halogen or a radical -OR ₂₄ or R ₁₅ and R ₁₆ together form a 1,3-butadiene-1,4-diyl radical, wherein R ₅ and Y have the meaning given above, and X ₁ and X _{2 are} independently -O- or -NR ₂₅ , and R _{21 is} hydrogen or C ₁ -C ₈ alkyl, and . R _{22 is} hydrogen or a group -X ₁ R ₂₆ , where X _{1 has} the meaning given above, and Z -0- or

and R ₂₃ C ₁ -C ₁₈ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₄ alkynyl, C ₅ -C ₇ cycloalkyl, C ₆ -C ₁₀ aryl, C ₇ -C ₁₄ aralkyl, C ₇ -C ₁₄ alkylphenyl or a group of the formula VI, and R _{24 is} hydrogen, optionally substituted by a group of the formula Vc, C ₁ -C ₈ alkyl, C ₅ -C ₇ cycloalkyl, C ₆ -C ₁₄ aryl, C ₇ -C ₁₄ aralkyl, C ₂ -C ₁₂ alkenyl; or an aliphatic C ₁ -C ₁₈ acyl group, aromatic C ₇ acyl group, araliphatic C ₈ -C ₉ acyl group or optionally substituted with chlorine, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, a Vc group and / or with hydroxy means C ₆ -C ₉ alicyclic acyl group, and R _{25 is} hydrogen, C ₁ -C ₁₈ alkyl, which may optionally be substituted by a group of the formula Vc, C ₃ -C ₆ alkenyl, C ₃ -C ₄ alkynyl, C ₅ -C ₇ cycloalkyl, C ₆ -C ₁₀ aryl , C ₇ -C ₁₄ aralkyl, a group of the formula CH ₂ -CH (R ₅ ) -OR ₂₆ or a Cr group of the formula VI, and R _{26 is} hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₆ alkenyl, cyclohexyl, benzyl or an aliphatic C ₁ - which is optionally substituted with chlorine, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy and / or with hydroxy C ₁₈ acyl group, aromatic -C ₇ acyl group, araliphatic C ₈ -C ₉ acyl group or alicyclic C ₆ -C ₉ acyl group, and _{R17 is} hydrogen, C ₁ -C ₁₈ alkyl, halogen, a group -OR ₂₄ or a group of the formula Vc, and R _{18 is} a group -N (R ₂₅ ) R ₂₇ and R _{19 is} hydrogen, or R _{18 and} R ₁₉ together are = 0 or = NR ₂₇ , and R _{20 is} hydrogen, C ₇ -C ₁₄ aralkyl, C ₇ -C ₁₄ alkylphenyl, or C ₁ -C ₁₈ alkyl, C ₂ -C ₁₂ alkenyl, C ₅ -C ₁₂ cycloalkyl or C _{6 which is} optionally substituted by a group of the formula Vc -C _{18 is} aryl, or if R ₁₈ and R ₁₉ together are -O- are a group of formula Va; or R20

of formula VII

means in which R ₁₅ , R ₁₆ , R ₁₈ and R ₁₉ have the meaning given above, and R _{28 is} C ₁ -C ₁₂ alkylene, butenylene, C ₆ -C ₁₀ arylene or diphenylene, means, and R _{27 is} hydrogen, C ₇ -C ₁₄ aralkyl, C ₇ -C ₁₄ alkylphenyl, hydroxy, or C ₁ -C ₁₈ alkyl, C ₂ -C ₁₂ alkenyl, C ₅ -C ₁₂ cycloalkyl or optionally substituted by a group of the formula Vc C ₆ -C _{14 is} aryl, or a group of the formula VI, or a group of the formula -CH ₂ -CH (R ₅ ) -OR ₂₆ ; or if R _{20 is} not a group of formula VII, R _{27 is} also a group of formula VIIIa or VIIIb

means in which R _{20 has} the meaning of R ₂₀ with the exception of the groups of the formula VII, and R ₁₅ , R ₁₆ , R ₂₅ and R _{28 have} the meaning given above. 3. New metal complexes according to claim 1 and 2 of formula I, wherein B as a single charged anion, for example, such an aliphatic or aromatic carboxylic acid, a phosphonic acid half-ester, a phosphinic acid, a _ph osphinigsäure or an enol of formula IX

wherein R _{29 is} alkyl, alkenyl, cycloalkyl, aralkyl or aryl, and. R _{30 is} hydrogen, alkyl, alkenyl, cycloalkyl, aralkyl, aryl or alkomycarbonyl, or R _{19 and} R ₃₀ together are optionally substituted 1,4-butadi-1,3-enylene or 1,4-butylene, and R ₃₁ optionally substituted alkyl, alkenyl, cyclc. alkyl, aralkyl, aryl, alkoxy or optionally substituted amino, and R _{32 is} oxo or optionally substituted imino, and the other symbols have the meanings given in claims 1 and 2. 4. New metal complexes according to claim 1 of formula XI

wherein M is Mg ²⁺ , VO ²⁺ , Ca ²⁺ , Mn ²⁺ , Zn ^{Z +} , Co ²⁺ , Ni ²⁺ or Al ³⁺ , and q is 2 or 3, and L _{1 is} a t-tooth group of the formula IVa, which is at least one group of the formulas Va, Vb or VI is substituted means and u is 0, 1 or 2, and t is 3, and R _{15 and} R ₁₆ independently of one another are hydrogen, C ₁ -C ₁₈ alkyl, which can optionally be substituted by a group of the formulas Va, Vb or Vc; or a group Vc, or a p-group of the formula VI, halogen or a radical -OR ₂₄ or R ₁₅ and R ₁₆ together form a 1,3-butadiene-1,4-dyl radical, where R _{5 is} hydrogen, methyl or phenyl, and Y is hydrogen, oxyl, C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ alkenyl, C ₃ -G ₆ alkynyl, C ₂ -C ₂₁ alkoxyalkyl, C ₇ -C ₉ aralkyl. 2,3-epoxypropyl, an aliphatic C ₁ -C ₄ acyl group or one of the groups -CH ₂ COOR ₆ , -CH ₂ -CH (R ₇ ) -OR ₈ , -COOR ₉ or -CONHR ₉ , wherein R _{6 is} C ₁ -C ₁₂ alkyl, C ₃ -C ₆ alkenyl, phenyl, C ₇ -C ₈ aralkyl or cyclohexyl and R _{7 is} hydrogen, methyl or phenyl, and R _{8 is} hydrogen, an aliphatic C ₁ -C ₁₈ acyl group, an aromatic C ₇ acyl group, an araliphatic C ₈ -C ₉ acyl group or an alicyclic C ₆ -C ₉ acyl group, the aromatic part optionally containing chlorine, C ₁ - C ₄ alkyl; C ₁ -C ₈ alkoxy and / or hydroxy may be substituted, and R _{9 is} C ₁ -C ₁₂ alkyl, cyclohexyl, phenyl or benzyl, and X ₁ and X _{2 are} independently -O- or -NR ₂₅ , and R _{21 is} hydrogen or C ₁ -C ₈ alkyl, and R ₂₂ denotes hydrogen or a group -X ₁ R ₂₆ , and 0 Z is -0- or -0-C-, and R ₂₃ C ₁ -C ₁₈ alkyl, C ₃ -C _b alkenyl, C ₃ -C ₄ alkynyl, C ₅ -C ₇ Cycloalkyl, C ₆ -C ₁₀ aryl, C ₇ -C ₁₄ aralkyl, C ₇ -C ₁₄ Alkylphenyl or a group of the formula VI in which Y and R _{21 have} the meaning given, and R _{24 is} hydrogen, optionally with a group of the formula Vc, in which X ₂ and R _{23 has} the meaning given, substituted C ₁ -C ₈ alkyl, C ₅ -C ₇ C ^y c ^l o-alkyl, C ₆ -C ₁₄ aryl , C ₇ -C ₁₄ aralkyl, C ₂ -C ₁₂ alkenyl; or an optionally chlorine-, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, a group Vc and / or hydroxy-substituted aliphatic C ₁ -C ₁₈ acyl group, aro- _{ma tic} C ₇ acyl group, araliphatic C ₈ - Is C ₉ acyl group or alicyclic C ₆ -C ₉ acyl group, and R _{25 is} hydrogen, C ₁ -C ₁₈ alkyl which may optionally be substituted by a group of the formula Vc in which X ₂ and R _{23 has} the meaning given, C ₃ -C ₆ alkenyl, C ₃ -C ₄ alkynyl, C ₅ -C ₇ cycloalkyl, C ₆ -C ₁₀ aryl, C ₇ -C ₁₄ aralkyl, a group of the formula CH ₂ -CH (R ₅ ) -OR ₂₆ or a group of the formula VI, and R _{26 is} hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₆ alkenyl, cyclohexyl, benzyl or an aliphatic C ₁ - which is optionally substituted with chlorine, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy and / or with hydroxy C ₁₈ acyl group, aromatic C ₇ acyl group, araliphatic C ₈ -C ₉ acyl group or alicyclic C ₆ -C ₉ acyl group, and Is 1 or 2, and m is a number from 0 to 3, the sum (3 q / r) + being equal to the coordination number of the metal ion M, and AH ₂ O or an amine of formula III, wherein R ₁₂ optionally substituted with -CH C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl, C ₆ -C ₁₈ aryl. C ₇ -C ₂₀ aralkyl, an optionally substituted aminoalkyl group or is a piperidinyl group, and R ₁₃ ^denotes hydrogen or C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl, optionally substituted with -OH, an optionally substituted aminoalkyl group or a piperidinyl group; or R _{12 and} R ₁₃ together with the N atom form a pyrrolidine, piperidine or morpholine ring which is substituted or unsubstituted by alkyl groups, and R _{14 is} hydrogen or C ₁ -C ₁₈ alkyl optionally substituted with -OH. 5. New metal complexes according to claim 1 of the formula

wherein M is Mg ²⁺ , Sr ²⁺ , VO ²⁺ , Ca ²⁺ , Mn ²⁺ , Zn ²⁺ , Co ²⁺ , Ni ²⁺ or Al ³⁺ , and q is 2 or 3, and L _{2 is} a t-toothed group of the formula IVb which is at least substituted by a group of the formulas Va, Vb or, and t is 2, and R _{15 and} R ₁₆ independently of one another are hydrogen, C ₁ -C ₁₈ alkyl, which can optionally be substituted by a group of the form Va, Vb or Vc; or a group Vc or a p-group of the formula halogen or a radical of the formula -OR ₂₄ or R ₁₅ and R ₁₆ together form a 1,3-butadiene-1,4-diyl radical, where R _{5 is} hydrogen, methyl or phenyl, and Y is hydrogen, oxyl, C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ alkenyl, C ₃ -C ₆ alkynyl, C ₂ -C ₂₁ alkoxyalkyl, C ₇ -C ₉ aralkyl, 2,3-epoxypropyl, an aliphatic C ₁ -C ₄ acyl group or one of the groups -CH ₂ COOR ₆ , -CH ₂ -CH (R ₇ ) -OR ₈ , Is -COOR ₉ or -CONHR ₉ , wherein ^R 6 is C ₁ -C ₁₂ alkyl, C ₃ -C ₆ alkenyl, phenyl, C ₇ -C ₈ aralkyl or cyclohexyl and R _{7 is} hydrogen, methyl or phenyl, and R _{8 is} hydrogen, an aliphatic C ₁ -C ₁₈ acyl group, an aromatic C ₇ acyl group, an araliphatic C ₈ -C ₉ acyl group or an alicyclic C ₆ -C ₉ acyl group, the aromatic part optionally containing chlorine, C ₁ -C ₄ alkyl, C ₁ -C ₈ alkoxy and / or hydroxy may be substituted, and R _{9 is} C ₁ -C ₁₂ alkyl, cyclohexyl, phenyl or benzyl, and X ₁ and X _{2 are} independently -0- or -NR ₂₅ , and R _{21 is} hydrogen or C ₁ -C ₈ alkyl, and R ₂₂ denotes Wasseratoff or a group X ₁ R ₂₆ , and Z is _-0 - or -OC-, and R ₂₃ C ₁ -C ₁₈ alkyl, C ₃ -C ₆ alkenyl, C3-C4 alkynyl, C ₅ -C ₇ cycloalkyl, C ₆ -C ₁₀ aryl, C ₇ -C ₁₄ aralkyl, C ₇ -C ₁₄ alkylphenyl or one Group of the formula VI means in which Y and R _{21 have} the meaning given, and R _{24 is} hydrogen, optionally with a group of the formula Vc, in which X ₂ and R _{23 has} the meaning given, substituted C ₁ -C ₈ alkyl, C ₅ -C ₇ cycloalkyl, C6-C14 aryl, C ₇ -C ₁₄ aralkyl, C ₂ -C ₁₂ alkenyl; or an aliphatic C ₁ -C ₁₈ acyl group, aromatic C ₇ acyl group, araliphatic C ₈ -C ₉ acyl group or optionally substituted with chlorine, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, a Vc group and / or with hydroxy means C ₆ -C ₉ alicyclic acyl group, and R _{25 is} hydrogen, C ₁ -C ₁₈ alkyl, which may optionally be substituted by a group of the formula Vc, in which X ₂ and R _{23 has} the meaning given, ^C ₃ - ^C ₆ alkenyl, C ₃ -C ₄ alkynyl, C ₅ -C ₇ cycloalkyl, C ₆ -C ₁₀ aryl, C ₇ -C ₁₄ aralkyl, a group of the formula CH ₂ -CH (R ₅ ) -OR ₂₆ or a group of the formula VI, and R _{26 is} hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₆ alkenyl, cyclohexyl, benzyl or an aliphatic C ₁ - which is optionally substituted with chlorine, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy and / or with hydroxy C ₁₈ acyl group, aromatic C ₇ acyl group, araliphatic C ₈ -C ₉ acyl group or alicyclic C ₆ -C ₉ acyl group, and R _{17 is} hydrogen, C ₁ -C ₁₈ alkyl, halogen, a group -OR ₂₄ or a group of the formula Vc, in which R ₂₃ , R ₂₄ and X ₂ have the meaning given, and r is 1, and m is a number from 0 to 2, the sum (2.q) + m being the coordination number of the metal ion M, and AH _{2 is} 0 or an amine of formula III, wherein R ₁₂ is C ₁ -C ₁₈ alkyl optionally substituted with -OH, C ₅ -C ₁₂ cycloalkyl, C ₆ -C ₁₈ aryl, C ₇ -C ₂₀ aralkyl, an optionally substituted aminoalkyl group or a piperidinyl group, and R _{13 is} hydrogen or C ₁ -C ₁₈ alkyl, C _S -C ₁₂ cycloalkyl, optionally substituted with -OH, an optionally substituted aminoalkyl group or a piperidinyl group, or R _{12 and} R ₁₃ together with the N atom form a pyrrolidine, piperidine or morpholine ring which is substituted or unsubstituted by alkyl groups, and R _{14 is} hydrogen or C ₁ -C ₁₈ alkyl optionally substituted with -OH. 6. New metal complexes according to claim 1 of the formula XYI

wherein M Mg ²⁺ , VO ²⁺ , Ca ²⁺ , Mn ²⁺ , Zn ²⁺ , Co ²⁺ , Ni ²⁺ or Al is ³⁺ and q is 2 or 3, and L _{3 is} a t-toothed group of the formula IVc which is substituted by at least one group of the formulas Va, Vb or VI, and t is 2 or 4, and R _{15 and} R ₁₆ independently of one another are hydrogen, C ₁ -C ₁₈ alkyl, which can optionally be substituted by a group of the formulas Va, Vb or Vc or a group Vc; or a p-group of the formula IV, halogen or a radical -OR ₂₄ , or R ₁₅ and R ₁₆ together form a 1,3-butadiene-1,4-diyl radical, where R _{5 is} hydrogen, methyl or phenyl, and Y is hydrogen, -oxyl, C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ alkenyl, C ₃ -C ₆ alkynyl, C ₂ -C ₂₁ alkoxyalkyl, C ₇ -C ₉ aralkgl , 2,3-epoxypropyl, an aliphatic C ₁ -C ₄ acyl group or one of the groups -CH ₂ COOR ₆ , -CH ₂ -CH (R ₇ ) -OR ₈ , -COOR ₉ or -CONHR ₉ , wherein R _{6 is} C ₁ -C ₁₂ alkyl, C ₃ -C ₆ alkenyl, phenyl, C ₇ -C ₈ aralkyl or cyclohexyl and R _{7 is} hydrogen, methyl or phenyl, and R _{8 is} hydrogen, an aliphatic C ₁ -C ₁₈ acyl group, an aromatic C ₇ acyl group, an araliphatic C ₈ -C ₉ acyl group or an alicyclic C ₆ -C ₉ acyl group meaning the aromatic part against _{can also be substituted} with chlorine, C ₁ -C ₄ alkyl, C ₁ -C ₈ alkoxy and / or hydroxy, and R ₉ C ₁ -C ₁₂ alkyl, cyclohexyl, phenyl or benzyl tet tet, and X ₁ and X _{2 are} independently -0- or -NR ₂₅ , and R _{21 is} hydrogen or C ₁ -C ₈ alkyl, and R _{22 represents} hydrogen or a group -X ₁ R ₂₆ , and Z is -0- or -0-C-, and R ₂₃ C ₁ -C ₁₈ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₄ alkynyl, C ₅ -C ₇ cycloalkyl, C ₆ -C ₁₀ aryl, C ₇ -C ₁₄ araltcyl, C ₇ -C ₁₄ alkylphenyl or a group of the formula VI in which Y and R _{21 have} the meaning given, and R _{24 is} hydrogen, optionally with a group of the formula Vc, in which X ₂ and R _{23 has} the meaning given, substituted C ₁ -C ₈ alkyl, C ₅ -C ₇ cycloalkyl, C ₆ -C ₁₄ aryl, C ₇ -C ₁₄ aralkyl, C ₂ -C ₁₂ alkeny or an aliphatic C ₁ -C ₁₈ acyl group optionally substituted with chlorine, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, a group Vc and / or with hydroxy, aromatic C ₇ Acyl group, araliphatic C ₈ -C ₉ acyl group or alicyclic C ₆ -C ₉ acyl group and R _{25 is} hydrogen, C ₁ -C ₁₈ alkyl, which may optionally be substituted by a group of the formula Vc, in which X ₂ and R _{23 has} the meaning given, C ₃ -C ₆ alkenyl, C ₃ -C ₄ alkynyl, C ₅ -C ₇ cycloalkyl, C ₆ -C ₁₀ aryl, C ₇ -C ₁₄ aralkyl, a group of the formula CH ₂ -CH (R ₅ ) -OR ₂₆ or a group of the formula V, and R _{26 is} hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₆ alkenyl, cyclo- hexyl, benzyl or an optionally substituted with chlorine, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy and / or with hydroxy substituted aliphatic C ₁ -C ₁₈ acyl group, aromatic C ₇ acyl group, araliphatic C ₈ -C ₉ acyl group or alicyclic C ₆ -C ₉ means acyl group, and R _{18 is} a group -N (R ₂₅ ) R ₂₇ , and ^R _{19 is} hydrogen, or R _{18 and} R ₁₉ together = 0 or = HR ₂₇ , and R _{20 is} hydrogen, C ₇ -C ₁₄ aralkyl, C ₇ -C ₁₄ alkylphenyl, or C ₁ -C ₁₈ alkyl, C ₂ -C ₁₂ alkenyl, C ₅ -C ₁₂ cycloalkyl or C _{6 which is} optionally substituted by a group of the formula Vc -C _{14 is} aryl, or a group of the formula VII or if R ₁₈ and R ₁₉ together = O are a group of the formula Va, where X ₁ , R ₂₁ and Y have the meaning defined above, and R _{28 is} C ₁ -C ₁₂ alkylene, .butenylene, C ₆ -C ₁₀ arylene or diphenylene, and R _{27 is} hydrogen, C ₇ -C ₁₄ aralkyl, C ₇ -C ₁₄ alkylphenyl, a group -OR ₂₄ , or C ₁ -C ₁₈ alkyl optionally substituted by a group of the formula Vc, C ₂ -C ₁₂ alkenyl, C ₅ - C _{12 is} cycloalkyl or C ₆ -C ₁₄ aryl, or a group of the formula VI, or a group of the formula -CH ₂ -CH (R ₅ ) -OR ₂₆ ; or if R _{20 is} not a group of formula VII; R ₂₇ also denotes a group of the formula VIIIa or VIIIb, and r is 1 or 2, and m is a number from 0 to 2, the sum (t * q / r) + m being the coordination number of the metal ion M, and AH ₂ O or an amine of formula III, wherein R ₁₂ is optionally substituted with -OH-substituted C ₁ -C ₁₈ alkyl, C ₅ - ^C ₁₂ cycloalkyl, C ₆ -C ₁₈ aralkyl, C ₇ -C ₂₀ aralkyl, an optionally substituted aminoalkyl group or a piperidinyl group, and R ₁₃ denotes hydrogen or C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl, optionally substituted with -OH, an optionally substituted aminoalkyl group or a piperidinyl group, or R _{12 and} R ₁₃ together with the N atom are a pyrrolidine which is substituted or unsubstituted by alkyl groups, Form piperidine or morpholine ring, and R _{14 is} hydrogen or C ₁ -C ₁₈ alkyl optionally substituted with -OH. 7, Use of the new metal complexes according to claim 1 as light stabilizers. 8. The organic material protected with the help of the new metal complexes according to claim 1. 9. A method for stabilizing organic material, characterized in that a new metal complex according to claim 1 is incorporated. 10. High molecular weight compounds, characterized in that they have, as a recurring structural unit, a building block of the composition of the formula I according to claim 1, in which r is 2.