EP0869171B1 - Metal complexes as bleach activators - Google Patents

Description

It is known that the bleaching power of peroxidic bleaching agents in laundry and cleaning agents, such as hydrogen peroxide, perborates, percarbonates, Persilicate and perphosphate and therefore the efficiency of these bleaching agents Removal of tea, coffee, fruit or red wine stains only at higher ones Temperatures of well over 60 ° C fully developed. To improve at lower temperatures, especially below 60 ° C, greatly reduced Bleaching action can be compounds to activate the peroxide bleach be used. For this purpose, a number of Transition metal salts or corresponding complexes with mostly chelating Compounds proposed, but the effectiveness of a metal or special combination of transition metal and complex ligand not predictable.

Such metal complexes for activating peroxy compounds are described in US 4728455, US 5314635, US 5244594, US 5114611, US 5114606, EP 549272, EP 544519, EP 544490, EP 544440, EP 509787, EP 458398, WO 9615136.

From J. Inorg. Nucl. Chem. 1975, vol. 37, pp. 2005 - 2006 are also neutral Metal complexes with bis- (2-hydroxybenzylidene) -2,6-pyridinediamine are known as ligands.

M

Mangan in der Oxidationsstufe II, III, IV, V und/oder VI oder Kobalt in der O Oxidationsstufe II und/oder III,

X

F^-, Cl^-, Br^-, SCN^-, OH^-, O₂ ^2-, O^2-, O₂ ^-, HOO^-, R⁹OO^-, H₂O, SH^-, CN^-, OCN^-, S^2-, N₃ ^-, NH₃, NR⁹ ₃, NR⁹ ₂ ^-, R⁹O^-, R⁹COO^-, R⁹SO₃ ^- und R⁹SO₄ ^-, ist wobei R⁹ jeweils Wasserstoff, C₁- bis C₈-Alkyl, Cycloalkyl oder C₆- bis C₁₈-Arylrest bedeutet,

Y

ein Gegenion in der entsprechenden stöchiometrischen Menge zum Ausgleich einer vorhandenen Ladung z, wobei

z

als Ladung des Metall-Komplexes positiv, null oder negativ sein kann,

n und m

unabhängig voneinander ganze Zahlen von 1 bis 4,

p

eine ganze Zahl von 0 bis 15,

q

z/Ladung von Y

L

einen Liganden der Formel (2)

bedeutet, wobei

R¹, R²

unabhängig voneinander Wasserstoff oder einen C₁- bis C₁₀-Alkylrest.

R³, R⁴, R⁵, R⁶, R⁷, R⁸

unabhängig voneinander Wasserstoff, C₁- bis C₃₀-Alkylreste, C₁- bis C₄-Alkoxygruppen, Amino- bzw. Ammoniumgruppen, Halogenatome, Sulfogruppen, Carboxylgruppen und die genannten Säuregruppen auch in Salzform vorliegen können,
ausgenommen Verbindungen der Formel 1 worin M = Mn, x = H₂O, z = Null und R¹, R², R³, R⁴, R⁵, R⁶, R⁷ und R⁸ Wasserstoff sind.

X

ist vorzugsweise eine der folgenden Gruppen:
F^-, Cl^-, Br^-, SCN^-, OH^-, O₂ ^2-, O^2-, O₂ ^-, HOO^-, R⁹OO^-, H₂O, SH^-, CN^-, OCN^-, S^2-, N₃ ^-, NH₃, NR⁹ ₃, NR⁹ ₂ ^-, R⁹O^-, R⁹COO^-, R⁹SO₃ ^- und R⁹SO₄ ^-, wobei R⁹ jeweils für Wasserstoff, C₁- bis C₈-Alkyl, Cycloalkyl oder C₆- bis C₁₈-Aryl steht. Das Gegenion Y ist vorzugsweise ein Ion der folgenden Formeln:

• bei positivem z: F^-, Cl^-, Br^-, NO₃-, ClO₄ ^-, SCN^-, PF₆ ^-, R⁹SO₄ ^-, R⁹COO^-, R⁹SO₃ ^-, BF₄ ^-, BPh₄ ^- und SO₄ ^2-;
• bei negativem z: Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Al³⁺, NH₄ ⁺, R⁹NH₃ ⁺, R⁹ ₂NH₂ ⁺, R⁹ ₃NH⁺ und R⁹ ₄N⁺,

wobei R⁹ die zuvor genannte Bedeutung hat.

M

ist vorzugsweise Mangan, R¹, R², R³, R⁴, R⁵ und R⁶ sind vorzugsweise eine der oben genannten Gruppen, ausgenommen Wasserstoff, und R⁷ und R⁸ sind vorzugsweise Wasserstoff.

The present invention relates to previously unknown compounds of the general formula 1 [L _n M _m X _p ] ^z Y _q in which

M

Manganese in oxidation level II, III, IV, V and / or VI or cobalt in O oxidation level II and / or III,

X

F ^- , Cl ^- , Br ^- , SCN ^- , OH ^- , O ₂ ^2- , O ^2- , O ₂ ^- , HOO ^- , R ⁹ OO ^- , H ₂ O, SH ^- , CN ^- , OCN ^- , S ^2- , N ₃ ^- , NH ₃ , NR ⁹ ₃ , NR ⁹ ₂ ^- , R ⁹ O ^- , R ⁹ COO ^- , R ⁹ SO ₃ ^- and R ⁹ SO ₄ ^- , where R ^{9 is in} each case hydrogen, C ₁ to C ₈ alkyl, cycloalkyl or C ₆ to C ₁₈ aryl radical,

Y

a counter ion in the corresponding stoichiometric amount to balance an existing charge z, where

z

as the charge of the metal complex can be positive, zero or negative,

n and m

independently of one another integers from 1 to 4,

p

an integer from 0 to 15,

q

z / charge of Y

L

a ligand of the formula (2)

means where

R ¹ , R ²

independently of one another hydrogen or a C ₁ - to C ₁₀ -alkyl radical.

R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸

independently of one another hydrogen, C ₁ - to C ₃₀ -alkyl radicals, C ₁ - to C ₄ -alkoxy groups, amino or ammonium groups, halogen atoms, sulfo groups, carboxyl groups and the acid groups mentioned can also be present in salt form,
except compounds of formula 1 wherein M = Mn, x = H ₂ O, z = zero and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 are} hydrogen.

X

is preferably one of the following groups:
F ^- , Cl ^- , Br ^- , SCN ^- , OH ^- , O ₂ ^2- , O ^2- , O ₂ ^- , HOO ^- , R ⁹ OO ^- , H ₂ O, SH ^- , CN ^- , OCN ^- , S ^2- , N ₃ ^- , NH ₃ , NR ⁹ ₃ , NR ⁹ ₂ ^- , R ⁹ O ^- , R ⁹ COO ^- , R ⁹ SO ₃ ^- and R ⁹ SO ₄ ^- , where R ⁹ each represents hydrogen, C ₁ - to C ₈ alkyl, cycloalkyl or C ₆ - to C ₁₈ aryl. The counter ion Y is preferably an ion of the following formulas:

• with positive z: F ^- , Cl ^- , Br ^- , NO ₃ -, ClO ₄ ^- , SCN ^- , PF ₆ ^- , R ⁹ SO ₄ ^- , R ⁹ COO ^- , R ⁹ SO ₃ ^- , BF ₄ ^- , BPh ₄ ^- and SO ₄ ^2- ;
• with negative z: Li ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , Al ³⁺ , NH ₄ ⁺ , R ⁹ NH ₃ ⁺ , R ⁹ ₂ NH ₂ ⁺ , R ⁹ ₃ NH ⁺ and R ⁹ ₄ N ⁺ ,

where R ^{9 has} the meaning given above.

M

is preferably manganese, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are preferably one of the groups mentioned above, except hydrogen, and R ⁷ and R ⁸ are preferably hydrogen.

The following compounds are particularly preferred:
Compounds of formula 1, wherein M is manganese in oxidation state II, III, IV, V or VI, m and n each represent the number 1 and p denotes an integer from 0 to 3, compounds of formula 1, wherein M is manganese in oxidation state II or III, m and n each represent the number 1 and p denotes an integer from 0 to 3, compounds of the formula 1, where M is manganese in oxidation state II, III, IV, V and / or VI m is the number 2, n is the number 1 or 2 and p is an integer from 0 to 5, compounds of the formula 1, where M is manganese in the oxidation state II and / or III, m is the number 2,
n stands for the number 1 or 2 and p stands for an integer from 0 to 5,
Compounds of formula 1, wherein M is cobalt in oxidation state II or III, m and n each represent the number 1 and p is an integer from 0 to 3 and compounds of formula 1, wherein M is cobalt in oxidation state II or III means m and n each represent the number 1 and p is zero.

The ligands of formula 2 are prepared by reacting salicylaldehyde and 2,6-diaminopyridine or their correspondingly substituted derivatives analogously to the information in J. Inorg. Nucl. Chem. 1975, vol. 37, pp. 2005 - 2006. The Production of the metal complexes according to the invention by reacting Mn or Co-salts with these ligands are also carried out analogously to the information given here Reference.

The mono- or polynuclear complexes of the general formula 1 according to the invention are excellent as bleaching and oxidation catalysts, especially in Detergents and cleaning agents and in textile and paper bleaching. Especially Textile detergents in the form of powder detergents or as liquid formulations and dish detergents. An advantage of Bleach catalysts according to the invention are their stability against hydrolysis and oxidation and their catalytic effect even at low temperatures. In such formulations, they not only improve the bleaching effect of Hydrogen peroxide, but also from organic and inorganic peroxy compounds.

The present invention accordingly also relates to a method for Bleaching soiled substrates, taking the soiled substrate in aqueous bleaching liquor with peroxy compounds and an effective amount of one or more of the metal complexes according to the invention as bleaching catalysts in Brings contact.

The aqueous bleaching liquor preferably contains these metal complexes based on the weight of the bleaching liquor, in an amount of 0.001 to 100 ppm Metal, especially 0.01 to 50 ppm metal, especially 0.03 to 20 ppm metal (ppm means parts per million based on weight). Higher levels Metal complexes, for example up to 500 ppm, can be used in industrial bleaching processes, for example in the textile or paper sector. The first mentioned low metal contents mainly refer to Household laundry detergents.

The invention also relates to the use of these bleach catalysts in bleaching detergents and cleaning agents. These detergents and cleaners contain in addition to a peroxide compound or a peroxide releasing Compound and the bleaching catalyst usually also surface-active Compounds and other known ingredients.

Suitable peroxides or peroxide-releasing compounds are Alkali metal peroxides, organic peroxides such as urea-hydrogen peroxide adducts, and inorganic persalts, such as the alkali perborates, percarbonates, -perphosphates, -persilicates and -persulfates. Are particularly preferred Sodium perborate tetrahydrate and especially sodium perborate monohydrate. Sodium perborate monohydrate is because of its good shelf life and its good solubility in water preferred. Sodium percarbonate can be made Environmental reasons may be preferred. Alkyl hydroperoxides are another suitable group of peroxide compounds. Examples of these substances are Cumene hydroperoxide and t-butyl hydroperoxide. Also aliphatic or aromatic Mono- or dipercarboxylic acids and the corresponding salts are suitable as Peroxy compounds. Examples include peroxy-α-naphthoic acid, Peroxylauric acid, peroxystearic acid, N, N-phthaloylaminoperoxycaproic acid, 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, Diperoxyisophthalic acid, 2-decyldiperoxybutane-1,4-diacid and 4,4'-sulphonylbisperoxybenzoic acid. Also suitable as peroxy compounds inorganic peroxyacid salts, e.g. B. Potassium monopersulfate. Mixtures of two or more of these compounds are also suitable.

The detergent and cleaning agent formulations according to the invention contain usually 1 to 30% by weight, in particular 2 to 25% by weight Peroxy compounds.

In addition to the peroxy compounds, the detergents and cleaning agents can additionally also so-called bleach activators in usual amounts (approx. 1 to 10 Wt .-%) included.

Examples of such bleach activators are compounds with quaternary Ammonium structures such as 2- (N, N, N-triethylammonio) ethyl-4-sulfophenyl carbonate, N-octyl-N, N-dimethyl-N-10-carbophenoxydecylammoniumchlorid, 3- (N, N, N-trimethylammonio) propyl sodium 4-sulfobenzoate and N, N, N-trimethylammonium toluyl-oxybenzenesulfonate.

In addition to the quaternary ammonium salts mentioned above, esters such as. B. Acylphenolsulfonate and the Acylalkylphenolsulfonate as well as Acylamide Bleach activator preferred. Of particular interest here are those in practice commonly used compounds sodium 4-benzoyloxybenzene sulfonate, N, N, N, N-tetraacetylethylenediamine (TAED), sodium 1-methyl-2-benzoyloxy-benzene-4-sulfonate, Sodium 4-methyl-3-benzoyloxybenzoate, sodium nonanoyloxybenzenesulfonate, Sodium 3,5,5-trimethylhexanoyloxybenzene sulfonate, benzoylcaprolactam, 2-phenyl-4H-3,1-benzoxazin-4-one, but glucose pentaacetate and tetraacetylxylose also ketones and nitrile activators.

Amounts are usually the effective amount of the metal complexes of the formula 1 from 0.0001 to 0.5% by weight of metal, in particular 0.00025 to 0.25% by weight of metal, especially 0.0005 to 0.1 wt .-% metal, based on the weight of the Formulations contained in these detergent and cleaning agent formulations. These quantities can fluctuate slightly depending on local custom.

The surface-active substance in the detergents and cleaning agents can be from Natural products, such as soap, or is synthetic Compound from the group of anionic, nonionic, amphoteric, (zwitterionic) or cationic surface-active substances, or Mixtures of these. Many suitable substances are commercially available, and are described in the literature, for example in "Surface active agents and detergents ", Vol. 1 and 2, by Schwartz, Perry and Berch. The total proportion of surface-active compounds can be up to 50% by weight, preferably 1 % By weight to 40% by weight, in particular 4% by weight to 25% by weight of the total Detergent or cleaning agents.

Synthetic anionic surfactants are common water-soluble alkali metal salts organic sulfates and sulfonates with alkyl radicals from about 8 to 22 carbon atoms, the term "alkyl" being the Includes alkyl substituents of higher aryl groups.

Examples of suitable anionic detergents are sodium and ammonium alkyl sulfonates, especially the sulfates obtained by sulfating higher (C ₈ to C ₁₈ ) alcohols; Sodium and ammonium alkylbenzenesulfonates with an alkyl radical from C ₉ to C ₂₀ , in particular linear secondary sodium alkylbenzenesulfonates with an alkyl radical from C ₁₀ to C ₁₅ ; Sodium alkyl glycerol ether sulfates, especially the esters of the higher alcohols derived from tallow and coconut oil; the sodium sulfates and sulfonates of the coconut fatty acid monoglycerides; Sodium and ammonium salts of the sulfuric acid esters of higher (C ₉ to C ₁₈ ) oxalkylated, especially the fatty alcohols alkoxylated with ethylene oxide; the reaction products of the esterification of fatty acids with isethionic acid and subsequent neutralization with sodium hydroxide; Sodium and ammonium salts of the fatty acid amides of methyl taurine; Alkane monosulfonates such as those from the reaction of α-olefins (C ₈ -C ₂₀ ) with sodium bisulfite and those from the reaction of paraffins with SO ₂ and Cl ₂ with subsequent basic hydrolysis, resulting in a mixture of different sulfonates; Sodium and ammonium dialkyl sulfosuccinates with alkyl radicals from C ₇ to C ₁₂ ; and olefin sulfonates which are formed in the reaction of olefins, in particular C ₁₀ - to C ₂₀ -α-olefins, with SO ₃ and subsequent hydrolysis of the reaction products. The preferred anionic detergents are sodium alkylbenzenesulfonates with alkyl radicals from C ₁₅ to C ₁₈ , and sodium alkyl ether sulfates with alkyl radicals from C ₈ to C ₁₈ .

Examples of suitable nonionic surface-active compounds, which are preferably used together with anionic surface-active compounds, are in particular the reaction products of alkylene oxides (usually ethylene oxide) with alkylphenols (alkyl radicals from C ₅ to C ₂₂ ), the reaction products generally 5 to 25 ethylene oxide (EO ) Units contained in the molecule; the reaction products of aliphatic (C ₈ to C ₁₈ ) primary or secondary, linear or branched alcohols with ethylene oxide, generally with 6 to 30 EO, and the addition products of ethylene oxide with reaction products of propylene oxide and ethylenediamine. Other nonionic surface active compounds are alkyl polyglycosides, long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulfoxides.

Amphoteric or zwitterionic surfactants can also be used can be used in the compositions according to the invention, but what is usually not desired because of its high cost. If amphoteric or zwitterionic compounds are used, so this usually happens in small amounts in compositions that are mainly anionic and contain nonionic surfactants.

Soaps can also be used in the compositions according to the invention, preferably in a proportion of less than 25% by weight. They are particularly suitable in small amounts in binary (soap / nonionic surfactant) or in ternary mixtures together with nonionic or mixed synthetic anionic and nonionic surfactants. The soaps used are preferably the sodium salts, and less preferably the potassium salts of saturated and unsaturated C ₁₀ to C ₂₄ fatty acids, or mixtures thereof. The proportions of such soaps can be from 0.5% by weight to 25% by weight, smaller amounts from 0.5% by weight to 5% by weight are generally sufficient for foam control. Soap contents between about 2% and about 20%, especially between about 5% and about 10%, have a positive effect. This is particularly the case in hard water, where the soap serves as an additional builder.

The detergents and cleaning agents generally also contain a builder. As Builders come into consideration: calcium-binding substances, precipitants, calcium-specific Ion exchangers and their mixtures. Examples of calcium binding Fabrics include alkali metal polyphosphates such as sodium tripolyphosphate; Nitrilotriacetic acid and its water-soluble salts; the alkali metal salts of Carboxymethyloxy succinic acid, ethylenediaminetetraacetic acid, Oxydisuccinic acid, mellitic acid, benzopolycarboxylic acids, citric acid; and Polyacetal carboxylates as disclosed in U.S. Pat. 4144226 and 4146495. Examples for precipitating agents are sodium orthophosphate, sodium carbonate and soaps long chain fatty acids.

Examples of ion exchangers that are specific for calcium are different types of water-insoluble, crystalline or amorphous Aluminum silicates, of which the zeolites are the best known representatives.

The builder substances can be present in amounts of 5% by weight to 80% by weight a proportion of 10% by weight to 60% by weight is preferred.

In addition to the ingredients already mentioned, the washing and Cleaning agents contain conventional additives in amounts that one usually found in such means. Examples of these are foaming agents, such as such as alkanolamides, especially the monoethanolamides from palm kernel oil fatty acids and coconut fatty acids; anti-foam substances such as Alkyl phosphates and silicones; Graying inhibitors and similar aids, such as such as sodium carboxymethyl cellulose and alkyl or substituted alkyl cellulose ethers; Stabilizers such as ethylenediaminetetraacetic acid; softener for textiles; inorganic salts such as sodium sulfate; and, usually small Quantities, fluorescent substances, perfumes, enzymes such as proteases, cellulases Lipases and amylases, disinfectants and dyes. The bleaching catalysts This invention can be used in a variety of products. This include textile detergents, textile bleaches, surface cleaners, Toilet cleaner, dishwasher cleaner, and also denture cleaner. The Detergents can be in solid or liquid form.

It is advantageous for reasons of stability and manageability To use bleach activators in the form of granules, in addition to the Bleach catalyst contain a binder. Different methods, such Producing granules are described in the patent literature, for example in Canada Pat. No. 1102966, GB 1561333, US 4087369, EP 240057, EP 241962, EP 101634 and EP 62523.

The granules containing the bleaching catalysts according to the invention are in the general of the detergent composition together with the others, dry ingredients such as enzymes, inorganic peroxide bleaches added. The detergent composition to which the catalyst granules added can be obtained in various ways, such as Mixing the dry components, extruding, spray drying.

In a further embodiment, the bleaching catalysts according to the invention are particularly suitable for non-aqueous liquid detergents, together with a bleaching peroxide compound, such as sodium perborate, around the detergent great cleaning ability for fabrics and textiles. such non-aqueous, liquid detergents, pasty and gelatinous detergents include compositions are, for example, in US 2864770, US 2940938, US 4772412, US 3368977, GB 1205711, GB 1370377, GB 1270040, GB 1292352, GB 2194536, DE 2233771, EP 28849. These are to compositions in the form of a non-aqueous liquid medium in which a solid phase can be dispersed. The non-aqueous, liquid medium can be a liquid, surface-active substance, preferably a nonionic surfactant, a non-polar liquid medium such as liquid Paraffin, a polar solvent, such as polyols, for example glycerol, Sorbitol, ethylene glycol, possibly in combination with low molecular weight monovalent Alcohols such as ethanol or isopropanol or mixtures thereof.

The solid phase can consist of builder substances, alkalis, abrasive substances, Polymers and solid ionic surface-active compounds, bleaches, fluorescent substances and other common solid ingredients.

The following examples are intended to provide an overview of the embodiments of the Give invention.

Example 1: Bis (3,5-ditert.butyl-2-hydroxybenzylidene) -2,6-pyridinediamine-manganese complex

A solution of 23.7 g of 3,5-ditert.butyl-2-hydroxybenzaldehyde in 100 ml of ethanol 5.57 g of 2,6-diaminopyridine were added and the solution obtained two Heated to reflux for hours. The precipitated solid became separated, washed with isopropanol and dried, 19.6 g Get bis (3,5-ditert.butyl-2-hydroxybenzylidene) -2,6-pyridinediamine. 3.25 g of so Compound obtained were in a mixture of 300 ml of ethanol and 105 ml Dimethylformamide dissolved and in portions 1.47 g of manganese (II) acetate (tetrahydrate) added. After stirring for two hours at the boil, the solvent was removed on Rotary evaporator (water jet vacuum) removed and the residue with ethanol washed. 3.60 g of bis (3,5-ditert.butyl-2-hydroxybenzylidene) -2,6-pyridinediamine-manganese complex were obtained in the form of a yellow-brown amorphous solid receive.

The following metal complexes are produced in an analogous manner. So much for this Containing metal complexes containing cobalt, these compounds were based on Cobalt (II) acetate produced in the form of the tetrahydrate:

Example 2: Bis (3,5-ditert.butyl-2-hydroxybenzylidene) -2,6-pyridinediamine-cobalt complex Example 3: Bis (2-hydroxybenzylidene) -2,6-pyridinediamine-manganese complex Example 4: Bis (2-hydroxy-benzylidene) -2,6-pyridinediamine-cobalt complex Example 5: Bis (2-hydroxy-3-methoxybenzylidene) -2,6-pyridinediamine-manganese complex Example 6: Bis (2-hydroxy-3-methoxybenzylidene) -2,6-pyridinediamine-cobalt complex Example 7: Bis (2-hydroxy-4-methoxybenzylidene) -2,6-pyridinediamine-manganese complex Example 8: Bis (2-hydroxy-4-methoxybenzylidene) -2,6-pyridinediamine-cobalt complex Example 9: Bis (2-hydroxy-4-diethylaminobenzylidene) -2,6-pyridinediamine-manganese complex Example 10: Bis (2-hydroxy-4-diethylaminobenzylidene) -2,6-pyridinediamine-cobalt complex Example 11: Bis (2-hydroxy-5-nitrobenzylidene) -2,6-pyridinediamine-manganese complex Example 12: Bis (2-hydroxy-5-nitrobenzylidene) -2,6-pyridinediamine-cobalt complex bleaching tests

A bleaching agent composition was prepared by combining 200 ml of an aqueous solution of reference detergent WMP (laundry research institute Krefeld, 5 g / l in water at 15 ° dH), 150 mg of sodium perborate monohydrate, 50 mg of tetraethylene diamine (TAED) and 2 mg of the respective catalyst. With this composition, pieces of tissue soiled with black tea (BC-1 tea on cotton, laundry research institute Krefeld) were subjected to a treatment at a temperature of 40 ° C. under isothermal washing conditions in a Linitest device (Heraeus). After a thirty minute wash, the fabric pieces were rinsed with water, dried and ironed; the bleaching effect was then quantified by determining the differences Δ R _{(KAT-TAED) of} the remissions before and after the bleaching using an ELREPHO 2000 whiteness measuring device (Datacolor). From these Δ R _(KAT-TAED) values and the Δ R _(TAED) values determined in control experiments without a bleaching catalyst, the ΔΔ R values listed in Table 1 were calculated, which are a direct measure of the improvement brought about by the addition of catalyst the bleaching effect: ΔΔ R = Δ R (Kat-TAED) - Δ R (TAED) Catalyst from example no. 1 2 3 4 5 6 7 8th 9 10 11 12 ΔΔ R 3.9 2.3 3.1 1.7 2.5 0.7 2.3 2.2 2.8 0.9 2.9 2.2

Further advantageous properties of the complexes described are low Color damage and minor fiber damage.

Claims (11)

1. A compound of the formula 1 [L_nM_mX_p]^zY_q in which

   M

   is manganese in oxidation stage II, III, IV, V and/or VI or cobalt in oxidation stage II and/or III,

   X

   is F^-, Cl^-, Br^-, SCN^-, OH^-, O₂ ^2-, O^2-, O₂ ^-, HOO^-, R⁹OO^-, H₂O, SH^-, CN^-, OCN^-, S^2-, N₃ ^-, NH₃, NR⁹ ₃, NR⁹ ₂ ^-, R⁹O^-, R⁹COO^-, R⁹SO₃ ^- and R⁹SO₄ ^-, in which R⁹ is in each case hydrogen, C₁- to C₈-alkyl, cycloalkyl or C₆- to C₁₈-aryl,

   Y

   is a counterion in the corresponding stoichiometric amount to balance a charge z present, where

   z

   as the metal complex charge, can be positive, zero or negative,

   n and m,

   independently of one another, are integers of from 1 to 4,

   p

   is an integer from 0 to 15,

   q

   is z/charge of Y

   L

   is a ligand of the formula (2)

   

   in which

   R¹, R²

   independently of one another are hydrogen or C₁- to C₁₀-alkyl,

   R³, R⁴, R⁵, R⁶, R⁷, R⁸,

   independently of one another, are hydrogen, C₁- to C₃₀-alkyl, C₁- to C₄-alkoxy groups, amino or ammonium groups, halogen atoms, sulfo groups, carboxyl groups, and the specified acid groups may also be in salt form, with the exception of compounds of the formula 1 in which M = Mn, x = H₂O, z = zero and R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are hydrogen.

2. A compound of the formula 1 as claimed in claim 1, in which X is F^-, Cl^-, Br^-, SCN^-, OH^-, O₂ ^2-, O^2-, O₂ ^- , HOO^-, R⁹OO^-, H₂O, SH^-, CN^-, OCN^-, S^2-, N₃ ^-, NH₃, NR⁹ ₃, NR⁹ ₂ ^-, R⁹O^-, R⁹COO^-, R⁹SO₃ ^- and R⁹SO₄ ^-, in which R⁹ is in each case hydrogen, C₁- to C₈-alkyl, cycloalkyl or C₆- to C₁₈-aryl.
3. A compound of the formula 1 as claimed in claim 1 in which the counterion Y is F^-, Cl^-, Br^-, NO₃ ^-, ClO₄ ^-, SCN^-, PF₆ ^-, R⁹SO₄ ^-, R⁹COO^-, R⁹SO₃ ^-, BF₄ ^-, BPh₄ ^-, and SO₄ ^2-; Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Al³⁺, NH₄ ⁺, R⁹NH₃ ⁺, R⁹ ₂NH₂ ⁺, R⁹ ₃NH⁺ and R⁹ ₄N⁺, and R⁹ is as defined in claim 2.
4. A compound of the formula 1 as claimed in claims 1 to 3, in which M is manganese in oxidation stage II, III, IV, V or VI, m and n are each 1 and p is an integer from 0 to 3.
5. A compound of the formula 1 as claimed in claims 1 to 3, in which M is manganese in oxidation stage II or III, m and n are each 1 and p is an integer from 0 to 3.
6. A compound of the formula 1 as claimed in claims 1 to 3, in which M is manganese in oxidation stage II, III, IV, V and/or VI, m is 2, n is 1 or 2 and p is an integer from 0 to 5.
7. A compound of the formula 1 as claimed in claims 1 to 3, in which M is manganese in oxidation stage II and/or III, m is 2, n is 1 or 2 and p is an integer from 0 to 5.
8. A compound of the formula 1 as claimed in claims 1 to 3, in which M is cobalt in oxidation stage II or III, m and n are each 1 and p is an integer from 0 to 3.
9. A compound of the formula 1 as claimed in claims 1 to 3, in which M is cobalt in oxidation stage II or III, m and n are each 1 and p is zero.
10. The use of the compound of the formula 1 as claimed in claim 1 as a bleach and oxidation catalyst.
11. The use of the compound of the formula 1 as claimed in claim 1 as a bleach and oxidation catalyst in laundry detergents and cleaning products and in textile and paper bleaching.