# Patent

## Title
Tris(heterocyclyl) metal complexes, washing and cleaning agents containing the same, and use as bleach catalysts

## Abstract

Tris(heterocyclyl)-metal complexes and the use thereof as bleach catalysts are described.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation of and claims benefit of priority under 35 U.S.C. §120 of International Application No. PCT/EP20081054347, filed on Apr. 10, 2008 (designating the U.S.), which in turn claims priority under 35 U.S.C. §119(a)-(d) of German Application No. DE 102007017657.2, filed on Apr. 12, 2007, the entire contents of each of which are incorporated herein by reference.


BACKGROUND OF THE INVENTION
For effective bleaching with hydrogen peroxide, the latter must be converted into a species having more bleaching activity. One possibility for generating activated peroxy compounds is the use of peracid precursors, so-called “bleach activators” such as TAED, that are converted by perhydrolysis into the active species.
A further possibility for generating activated species is enzymatically catalyzed perhydrolysis of carboxylic acid esters or nitrile compounds using perhydrolases.
Lastly, it is also known to use bleach catalysts to generate activated species, a “bleach catalyst” being understood as a substance that can improve the bleaching performance of hydrogen peroxide on a bleachable material without itself participating stoichiometrically in the reaction.
The use of bleach catalysts has the advantage, as compared with the other bleach activation methods, that substoichiometric quantities of the compound are sufficient, with the result that space and weight can be saved in the formulation of the bleach-containing product. In addition, the reduction in weight, especially in the context of washing and cleaning applications, is also associated with the advantage that less material is discharged into the environment, which is particularly advantageous for ecological reasons. Transportation and packaging costs can also be reduced as a result.
Consideration must also be given to the fact that premature hydrolysis can occur when bleach activators such as nitrites or TAED are used in the presence of water, whereas this problem can be very largely eliminated with the use of bleach catalysts. Furthermore, the production of acids that occurs in the context of noncatalytic bleach activation based on peracids causes a shift in pH that can have an unfavorable effect on bleaching performance. In addition, the bleaching performance of most bleach activators at low temperatures is often unsatisfactory.
For the reasons cited above, the use of bleach catalysts is of particular interest as compared with the other techniques for bleach activation, so that a demand exists in principle for novel bleach catalysts.
Bleach catalysts that have been described are, in particular, metal complexes of organic ligands such as salenes, saidimines, tris[salicylideneaminoethyl]amines, monocyclic polyazaalkanes, cross-bridged polycyclic polyazaalkanes, terpyridines, and tetraamido ligands. A disadvantage of the metal complexes just described is, however, they either they do not possess sufficient bleaching performance especially at low temperature, or that, with sufficient bleaching performance, undesirable damage occurs to colors and, in some cases, also to textile fibers.
Some of the tris(heterocyclyl) ligands and metal ligand complexes usable according to the present invention are already known in the existing art. For example, Brown et al. (J. Am. Chem. Soc. 103 (1981) 6953-6959) and Kimblin et al. (J. Chem. Soc., Chem. Commun. (1995) 1813-1815) describe tris(imidazolyl)phosphines and -carbinols and their use, in particular in complex with zinc(II), as a model for the active center of the enzyme carbonic anhydrase. Ruther et al. (J. Chem. Soc., Dalton Trans. (2002) 4684-4693) describe chromium(III) and vanadium(III) complexes of tris(imidazolyl)phosphines and -alkanes and their use to catalyze the reaction of ethylene to 1-alkenes or polymers. Brown et al. (Inorganica Chimica Acta 108 (1985) 201-207) describe Co(II) complexes, and Schiller et al. (Inorg. Chem. 44 (2005) 6482-6492) describe Cu(II) complexes, of tris(imidazolyl)phosphines and their use for catalyzing the hydrolysis of phosphate esters. Allen et al. (Inorg. Chem. 36 (1997) 1732-1734) describe copper(II) complexes, and Vankai et al. (Inorg. Chem. 31 (1992) 343-345) describe iron(II)/(III) complexes, of tris(imidazolyl)phosphines and their use to hydroxylate alkanes. Sorrell et al. (Inorg. Chem. 34 (1995) 952-960) describe copper(I) complexes of tris(imidazolyl)phosphines and their use as a model for the active center of copper-containing enzymes. Wu et al. (Inorg. Chem. 29 (1990) 5174-5183) describe iron(III) and manganese(III) complexes of tris(imidazolyl)phosphines. Kurtz (Chem. Rev. 90 (1990) 585-606) describes iron complexes of tris(imidazolyl)phosphines and their structural characterization. Enders et al. (Z. Anorg. Allg. Chem. 630 (2004) 1501-1506) describe lithium, copper, silver, and scandium complexes of tris(imidazolyl)phosphines.
Byers et al. (J. Organometallic Chemistry 385 (1990) 417-427; J. Chem. Soc., Chem. Commun. (1988) 639-641) describe methane trisubstituted with heterocycles, as well as Pd(II) complexes of those ligands. Sorrell et al. (J. Am. Chem. Soc. 109 (1987) 4255-4260) describe a complex of Cu(I) and methoxymethane trisubstituted with imidazole derivatives, as a model of hemocyanin.
Keene et al. (Inorganica Chimica Acta 187 (1991) 217-220; Inorg. Chem. 27 (1988) 2040-2045) describe central atoms trisubstituted with pyridine, as well as Ru(II) complexes of those ligands. Kuo et al. (J. Organometallic Chemistry 588 (1999) 260-267) describe complexes of tris(2-pyridyl)phosphines and transition metals of the sixth group of the periodic table, as well as a structural investigation thereof. Anderson et al. (J. Chem. Soc., Dalton Trans. (2000) 3505-3512) describe phosphine oxide and methane trisubstituted with heterocycles, as well as iron complexes of those ligands. Adam et al. (J. Chem. Soc., Dalton Trans. (1997) 519-530) describe cobalt complexes of tris(2-pyridyl)methane and tris(2-pyridyl)phosphine. Astley et al. (J. Chem. Soc., Dalton Trans. (1996) 1845-1851) describe central atoms trisubstituted with pyridine, as well as nickel and zinc complexes of those ligands. Kurtev et al. (J. Chem. Soc., Dalton Trans. (1980) 55-57) describe Ru(II) and Rh(I) complexes of tris(2-pyridyl)phosphine and use of the rhodium complexes for hydroformylation reactions. Astley et al. (J. Chem. Soc. Dalton Trans. (1995) 3809-3818) describe copper and zinc complexes of tris(2-pyridyl)phosphines.
WO 2004/014052 discloses central atoms trisubstituted with heterocycles, as well as metal complexes of those ligands with metals of groups 3, 4, 5, or 6 of the periodic table, and the use of said metal complexes as polymerization catalysts.
The use of tris(heterocyclyl)-metal complexes as bleach catalysts is already disclosed, for example, in DE10163331, DE19713851, and JP08300624. Here, however, the heterocycles are bound to the central atom of the ligand not directly, but instead via an alkylene bridge. It has been found, however, to be particularly advantageous that the heterocycles are bound directly to the central atom of the ligand, without an intermediate bridge.
BRIEF SUMMARY OF THE INVENTION
The present invention relates to tris(heterocyclyl)-metal complexes and to the use thereof as bleach catalysts.
It has now been found, surprisingly, that complexes of tris(heterocyclyl) ligands and transition metals constitute effective bleach catalysts, and simultaneously behave more gently toward laundry than presently usual bleach catalysts.
A first subject of the present invention is therefore washing and cleaning agents containing ligands and/or metal-ligand complexes of ligands of the general formula (I)

X[-Het]3  (I)

wherein

    
    
        X denotes N, N(+)—R1, P, P(+)—R1, P(O), B, B(−)—R1, C—R2, or Si—R2,
        Het denotes any optionally substituted nitrogen-containing heterocycle,
        wherein the nitrogen-containing heterocycle can correspondingly be a monocyclic or multicyclic aromatic or aliphatic heterocycle,
        R1 and R2 denote hydrogen or any substituent, and
        wherein the nitrogen-containing heterocycle is preferably bound to X in an alpha position with reference to a (or, when only one nitrogen atom is present, with reference to the) nitrogen atom that is contained.
    
    


In a preferred embodiment, the ligand according to the present invention is a ligand of the general formula (II)




denotes any optionally substituted nitrogen-containing heterocycle having a —C═N group, selected in particular from optionally substituted pyridine, pyrimidine, pyrazine, triazine, imidazole, thiazole, oxazole, pyrazole, 1,2,3-triazole, 1,2,4-triazole, quinoline, isoquinoline, benzimidazole, benzthiazole, benzoxazole, or purine, as well as mono- or polyhydrogenated representatives of said compounds.

Some of the nitrogen-containing heterocycles usable in preferred fashion according to the present invention are depicted below:




In a further preferred embodiment, the ligand according to the present invention is a ligand of the general formula (III)




denotes an optionally substituted heterocycle having an aromatically stabilized nitrogen anion, selected in particular from optionally substituted pyrrolate, imidazolate, pyrazolate, indolates, isoindolate, benzimidazolate, and purinate, as well as optionally mono- or polyhydrogenated representatives of said compounds.

The fact that the heterocycle is bound in an alpha position with reference to a nitrogen atom that is contained means, for example, that pyrrole can be bound to X in position 2 or 5, imidazole in position 2, 4 or 5, thiazole in position 2 or 4, pyridine in position 2 or 6, pyrimidine in position 2, 4 or 6, quinoline in position 2, isoquinoline in position 1 or 3, indole in position 2, and isoindole in position 1 or 3.
In an embodiment particularly preferred according to the present invention, X denotes N, P, or P(O).
In a further embodiment particularly preferred according to the present invention, Het denotes a monocyclic 5- or 6-membered, or a bicyclic 9- or 10-membered, optionally substituted nitrogen-containing heterocycle that is bound to X in an alpha position with reference to a nitrogen atom that is contained, wherein this embodiment preferably also refers to a ligand according to formula (II) or (III).
In a further embodiment particularly preferred according to the present invention,
X denotes N or P, and
Het denotes optionally substituted imidazole or benzimidazole.
In a further particularly preferred embodiment, the ligand is a ligand of the general formula (IV)




or of the general formula (V)





wherein R denotes hydrogen or optionally substituted alkyl, in particular C1-18 alkyl, and wherein the heterocycle can also optionally be substituted.



DETAILED DESCRIPTION OF THE INVENTION
“Optionally substituted” means, for purposes of the present invention, that the respective residue, and in particular the heterocycle, can carry at least one, by preference one, two, or three, substituents.
The substituents, and in particular R1 and R2, are selected according to the present invention in particular from alkyl, in particular C1-22 alkyl, by preference C1-18 alkyl, trifluormethyl, cycloalkyl, in particular C3-8 cycloalkyl, cycloalkylalkyl, in particular C3-8 cycloalkyl-C1-12 alkyl, alkenyl, in particular C2-18 alkenyl, alkinyl, in particular C2-18 alkinyl, heteroalkyl, heterocycloalkyl, alkoxy, in particular C1-18 alkoxy, alkylsulfanyl, in particular C1-18 alkylsulfanyl, alkylsulfinyl, in particular C1-18 alkylsulfinyl, alkylsulfonyl, in particular C1-18 alkylsulfonyl, alkanoyl, in particular C1-18 alkanoyl, alkanoyloxy, in particular C1-18 alkanoyloxy, alkoxycarbonyl, in particular C1-18 v alkoxycarbonyl, alkylaminocarbonyl, in particular C1-18 alkylaminocarbonyl, alkylsulfanylcarbonyl, in particular C1-18 alkylsulfanylcarbonyl, hydroxy, amino, aryl, in particular C6-10 aryl, arylalkyl, in particular C6-10 aryl-C1-12 alkyl, aryloxy, in particular C6-10 aryloxy, arylsulfanyl, in particular C6-10 arylsulfanyl, arylsulfinyl, in particular C6-10 arylsulfinyl, arylsulfonyl, in particular C6-10 arylsulfonyl, arylcarbonyl, in particular C6-10 arylcarbonyl, arylcarbonyloxy, in particular C6-10 arylcarbonyloxy, aryloxycarbonyl, in particular C6-10 aryloxycarbonyl, arylaminocarbonyl, in particular C6-10 arylaminocarbonyl, arylsulfanylcarbonyl, in particular C6-10 arylsulfanylcarbonyl, heteroaryl, heteroarylalkyl, in particular heteroaryl-C1-12 alkyl, heteroaryloxy, heteroarylamino, heteroarylsulfanyl, heteroarylsulfonyl, heteroarylsulfoxidyl, heteroarylcarbonyl, heteroarylcarbonyloxy, heteroaryloxycarbonyl, heteroarylaminocarbonyl, heteroarylsulfanylcarbonyl, alkoxysulfonyl, in particular C1-18 alkoxysulfonyl, alkoxycarbinol, in particular C1-12 alkoxycarbinol, ammonium, hydroxycarbonyl, alkoxycarbonyl, in particular C6-18 alkoxycarbonyl, aryloxycarbonyl, in particular C6-10 aryloxycarbonyl, amidocarbonyl, halogen, in particular chlorine, bromine, iodine or fluorine, nitro, sulfato, sulfo, amidosulfo, phosphato, phosphono, amidophosphono, formyl, thioformyl, —(CH2—CH2—O—)nH, and —(CH2—CH2—CH2—O)nH where n=1 to 20, by preference 3 to 20, wherein all residues of the molecule thus resulting, in particular the aliphatic and aromatic residues, mutually independently in each case, can optionally also be mono- or poly-, in particular mono-, di-, or tri-, by preference monosubstituted, in particular with substituents selected from the aforementioned residues.
In a preferred embodiment, the substituents, and in particular R1, denote, mutually independently, hydrogen, alkyl, in particular C1-22 alkyl, by preference C1-18 alkyl, cycloalkyl, in particular C3-8 cycloalkyl, cycloalkylalkyl, in particular C3-8 cycloalkyl-C1-12 alkyl, alkenyl, in particular C2-18 alkenyl, alkinyl, in particular C2-18 alkinyl, heteroalkyl, heterocycloalkyl, alkanoyl, in particular C1-18 alkanoyl, alkoxycarbonyl, in particular C1-18 alkoxycarbonyl, alkylaminocarbonyl, in particular C1-18 alkylaminocarbonyl, alkylsulfanylcarbonyl, in particular C1-18 alkylsulfanylcarbonyl, aryl, in particular C6-10 aryl, arylalkyl, in particular C6-10 aryl-C1-12 alkyl, arylcarbonyl, in particular C6-10 arylcarbonyl, aryloxycarbonyl, in particular C6-10 aryloxycarbonyl, arylaminocarbonyl, in particular C6-10 arylaminocarbonyl, arylsulfanylcarbonyl, in particular C6-10 arylsulfanylcarbonyl, heteroaryl, heteroarylalkyl, in particular heteroaryl-C1-12 alkyl, heteroarylcarbonyl, heteroaryloxycarbonyl, heteroarylaminocarbonyl, heteroarylsulfanylcarbonyl, trifluormethyl, formyl, —(CH2—CH2—O—)nH, or —(CH2—CH2—OH2—O)nH where n=1 to 20, wherein all residues of the molecule thus resulting, in particular the aliphatic and aromatic residues, mutually independently in each case, can optionally also be mono- or poly-, in particular mono-, di-, or tri-, by preference monosubstituted, in particular with substituents selected from the aforementioned residues and selected from ammonium, hydroxycarbonyl, alkoxycarbonyl, in particular C1-18 alkoxycarbonyl, aryloxycarbonyl, in particular C6-10 aryloxycarbonyl, amidocarbonyl, halogen, in particular chlorine, bromine, iodine, or fluorine, nitro, sulfato, sulfo, amidosulfo, phosphate, phosphono, amidophosphono, hydroxy, alkoxy, in particular C1-18-alkoxy, amino and alkanoyloxy, in particular C1-18 alkanoyloxy.
In a very particularly preferred embodiment, the ligands are selected from (optionally mono- or polysubstituted) tris(imidazol-2-yl)phosphine (htimp), tris(1-methylimidazol-2-yl)phosphine (timp), tris(1,4,5-trimethylimidazol-2-yl)phosphine (ttmimp), tris(1-methylbenzimidazol-2-yl)phosphine (tbimp), and tris(pyridin-2-yl)phosphine.
“C1-18 alkyl” denotes according to the present invention, mutually independently in each case, all saturated linear and branched alkyl residues having up to 18 carbon atoms, C1-6 alkyl residues being preferred. “C1-6 alkyl” denotes according to the present invention all saturated linear and branched alkyl residues having up to 6 carbon atoms, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and all isomers of pentyl and hexyl.
“C3-8 cycloalkyl” denotes according to the present invention, mutually independently in each case, all cyclic alkyl residues having 3 to 8 carbon atoms, by preference having 5 to 6 carbon atoms, wherein the residues can be saturated or unsaturated, in particular cyclopentyl, cyclohexyl, or cyclopentadienyl.
“C2-18 alkenyl” denotes according to the present invention, mutually independently in each case, all linear and branched alkyl residues, having up to 18 carbon atoms, that contain at least one double bond, C2-6 alkenyl residues being preferred. “C2-6 alkenyl” denotes according to the present invention all linear and branched alkyl residues, having up to 6 carbon atoms, that contain at least one double bond, in particular ethenyl, propenyl, isopropenyl, and all isomers of butenyl, pentenyl, and hexenyl.
“C2-18 alkinyl” denotes according to the present invention, mutually independently in each case, all linear and branched alkyl residues, having up to 18 carbon atoms, that contain at least one triple bond, C2-6 alkinyl residues being preferred. “C2-6 alkinyl” denotes according to the present invention all linear and unbranched alkyl residues, having up to 6 carbon atoms, that contain at least one triple bond, in particular ethinyl, propinyl, isopropinyl, and all isomers of butinyl, pentinyl, and hexinyl.
“Heteroalkyl” denotes according to the present invention, mutually independently in each case, all saturated and mono- or polyunsaturated, linear or branched alkyl residues that contain at least one, preferably exactly one, heteroatom, selected in particular from O, S, and N, the sum of carbon atoms and heteroatoms preferably equaling up to 18, particularly preferably up to 6.
“Heterocycloalkyl” denotes according to the present invention, mutually independently in each case, all cyclic alkyl radicals that contain at least one, preferably exactly one, heteroatom, selected in particular from O, S, and N, the ring having by preference three to eight members, particularly preferably five to six members. Examples thereof are tetrahydrofuranyl, tetrahydrothiophenyl, pyrrolidinyl, 2-thiazolinyl, tetrahydrothiazolyl, tetrahydrooxazolyl, piperidinyl, piperazinyl, morpholinyl, and thiomorpholinyl.
“C1-18 alkoxy” denotes according to the present invention, mutually independently in each case, all saturated and unsaturated, linear and branched alkyl residues, having up to 18 carbon atoms, that are bound via an oxygen atom, C1-6 alkoxy residues being preferred. “C1-6 alkoxy” denotes according to the present invention, mutually independently in each case, all saturated and unsaturated, linear and branched alkyl residues, having up to 6 carbon atoms, that are bound via an oxygen atom, in particular methoxy and ethoxy.
“C1-18 alkylsulfanyl” denotes according to the present invention, mutually independently in each case, all saturated and unsaturated, linear and branched alkyl residues, having up to 18 carbon atoms, that are bound via a sulfur atom, C1-6 alkylsulfanyl residues being preferred. “C1-6 alkylsulfanyl” denotes according to the present invention all saturated and unsaturated, linear and branched alkyl residues, having up to 6 carbon atoms, that are bound via a sulfur atom, in particular methylsulfanyl and ethylsulfanyl.
“C1-18 alkylsulfinyl” denotes according to the present invention, mutually independently in each case, all saturated and unsaturated, linear and branched alkyl residues, having up to 18 carbon atoms, that are bound via an SO— group, C1-6 alkylsulfonyl residues being preferred. “C1-6 alkylsulfinyl” denotes according to the present invention all saturated and unsaturated, linear and branched alkyl residues, having up to 6 carbon atoms, that are bound via an SO— group, in particular methylsulfinyl and ethylsulfinyl.
“C1-18 alkylsulfonyl” denotes according to the present invention, mutually independently in each case, all saturated and unsaturated, linear and branched alkyl residues having up to 18 carbon atoms that are bound via an SO2— group, C1-6 alkylsulfoxidyl residues being preferred. “C1-6 alkylsulfonyl” denotes according to the present invention all saturated and unsaturated, linear and branched alkyl residues, having up to 6 carbon atoms, that are bound via an SO2— group, in particular methylsulfonyl and ethylsulfonyl.
“C1-18 alkanoyl” denotes according to the present invention, mutually independently in each case, all saturated and unsaturated, linear and branched alkyl residues, having up to 18 carbon atoms, that are bound via a carbonyl group, C1-6 alkanoyl residues being preferred. “C1-6 alkanoyl” denotes according to the present invention all saturated and unsaturated, linear and branched alkyl residues, having up to 6 carbon atoms, that are bound via a carbonyl group, in particular methylcarbonyl and ethylcarbonyl.
“C1-18 alkanoyloxy” denotes according to the present invention, mutually independently in each case, all saturated and unsaturated, linear and branched alkyl residues, having up to 18 carbon atoms, that are bound via a carbonyloxy group, C1-6 alkanoyloxy residues being preferred. “C1-6 alkanoyloxy” denotes according to the present invention all saturated and unsaturated, linear and branched alkyl residues, having up to 6 carbon atoms, that are bound via a carbonyloxy group, in particular methanoyloxy, ethanoyloxy, n-propanoyloxy, and i-propanoyloxy.
“C1-18 alkoxycarbonyl” denotes according to the present invention, mutually independently in each case, all saturated and unsaturated, linear and branched alkyl residues, having up to 18 carbon atoms, that are bound via an oxycarbonyl group, C1-6 alkoxycarbonyl residues being preferred. “C1-6 alkoxycarbonyl” denotes according to the present invention all saturated and unsaturated, linear and branched alkyl residues, having up to 6 carbon atoms, that are bound via an oxycarbonyl group, in particular methoxycarbonyl and ethoxycarbonyl.
“C1-18 alkylaminocarbonyl” denotes according to the present invention, mutually independently in each case, an aminocarbonyl group that is mono- or polysubstituted with a saturated or unsaturated, linear or branched alkyl residue having up to 18 carbon atoms, wherein aminocarbonyl residues mono- or disubstituted with C1-6 alkyl groups, in particular monomethylaminocarbonyl, diemethylaminocarbonyl, monoethylaminocarbonyl, and diethylaminocarbonyl, are preferred.
“C1-18 alkylsulfanylcarbonyl” denotes according to the present invention, mutually independently in each case, all saturated and unsaturated, linear and branched alkyl residues, having up to 18 carbon atoms, that are bound via a thiocarbonyl group, C1-6 alkylsulfanylcarbonyl radicals being preferred. “C1-6 alkylsulfanylcarbonyl” denotes according to the present invention all saturated and unsaturated, linear and branched alkyl residues, having up to 6 carbon atoms, that are bound via a thiocarbonyl group, in particular methylthiocarbonyl and ethylthiocarbonyl.
“(C1-18 alkyl)NH” denotes according to the present invention, mutually independently in each case, all saturated and unsaturated, linear and branched alkyl residues, having up to 18 carbon atoms, that are bound via a hydrogen-amino group, (C1-6 alkyl)NH being preferred. “(C1-6-Alkyl)NH” denotes according to the present invention all saturated and unsaturated, linear and branched alkyl residues, having up to 6 carbon atoms, that are bound via a hydrogen-amino group, in particular CH3NH and C2H5NH.
“Di-(C1-18 alkyl)N” denotes according to the present invention, mutually independently in each case, all saturated and unsaturated, linear and branched alkyl residues, having up to 18 carbon atoms, that are bound via a (C1-18 alkyl)amino group, di-(C1-6 alkyl)N being preferred. The two alkyl residues can, in this context be identical to or different from one another. “Di-(C1-6 alkyl)N” denotes according to the present invention all saturated and unsaturated, linear and branched alkyl residues, having up to 6 carbon atoms, that are bound via a (C1-6 alkyl)amino group, in particular (CH3)2N and (C2H5)2N.
“C6-10 aryl” denotes according to the present invention preferably phenyl or naphthyl, particularly preferably naphthyl, in particular including in C6-10 aryl-C1-42 alkyl, C6-10 aryloxy, C6-10 arylamino, C6-10 arylsulfanyl, C6-10 arylsulfonyl, C6-10 arylsulfoxidyl, C6-10 arylcarbonyl, C6-10 arylcarbonyloxy, C6-10 aryloxycarbonyl, C6-10 arylaminocarbonyl, C6-10 arylsulfanylcarbonyl.
“Heteroaryl” denotes according to the present invention, unless otherwise indicated, an aromatic residue containing at least one heteroatom selected from O, S, and N, having 5 to 10, by preference 5 or 6 ring members, by preference selected from furanyl, thienyl, thiophenyl, pyrrolyl, isopyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, isothiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, benzofuranyl, benzothiophenyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, indazolyl, pyridofuranyl, and pyridothienyl, in particular including in heteroaryl-C1-12 alkyl, heteroaryloxy, heteroarylamino, heteroarylsulfanyl, heteroarylsulfonyl, heteroarylsulfoxidyl, heteroarylcarbonyl, heteroarylcarbonyloxy, heteroaryloxycarbonyl, heteroarylaminocarbonyl und heteroarylsulfanylcarbonyl.
In C6-10 aryl-C1-12 alkyl and heteroarylalkyl, the alkyl residue can be saturated or unsaturated, branched or unbranched. Preferred residues are benzyl, phenylethyl, naphthylmethyl, and naphthylethyl.
“Amino” denotes according to the present invention any substituted or unsubstituted amino group, in particular —NH2, —NH(C1-18 alkyl), —N(C1-18 alkyl)2, —NH(C6-10 aryl), or —N(C6-10 aryl)2.
“Ammonium” denotes according to the present invention any substituted or unsubstituted ammonium group, in particular —NH3(+), —NH2(C1-18 alkyl)(+), —NH(C1-18 alkyl)2(+), or —N(C1-18 alkyl)3(+).
“Sulfato” denotes according to the present invention, in particular, —O—S(O)2—O—R, “sulfo” denotes —S(O)2—O—R, “amidosulfo” denotes —O—S(O)2—NR2, “phosphato” denotes O—P(O)(OR)2, “phosphono” denotes —P(O)(OR)2, “amidophosphono” denotes —O—P(O)(NR2)2 or —O—P(O)(OR)(NR2), and “amidocarbonyl” denotes —C(O)—NR2, wherein R, mutually independently in each case, denotes H, M(+), C1-18 alkyl, C6-10 aryl, or C1-18 alkyl-C6-10 aryl.
In an embodiment particularly preferred according to the present invention, in order to enhance solubility the skeleton carries at least one residue encompassing at least one group selected from ammonium, nitro, sulfato, sulfo, amidosulfo, hydroxycarbonyl, alkoxycarbonyl, aryloxycarbonyl, amidocarbonyl, phosphato, phosphono, amidophosphono, hydroxy, alkoxy, amino, polyoxyethylene, and halogen as substituents, wherein the residue can in this context be selected in particular from sulfo, sulfoalkyl, in particular sulfo-C1-18 alkyl, hydroxycarbonyl, hydroxycarbonylalkyl, in particular hydroxycarbonyl-C1-18 alkyl, phosphono, phosphonoalkyl, in particular phosphono-C1-18 alkyl, hydroxy, hydroxyalkyl, in particular hydroxy-C1-18 alkyl, amino, aminoalkyl, in particular amino-C1-48 alkyl, halogen, haloalkyl, in particular halo-C1-18 alkyl, —(CH2—CH2—O—)nH, and C1-18 alkyl-(CH2—CH2—O—)nH, where n=1 to 20, by preference 3 to 20, in each case.
The metal-ligand complex according to the present invention is by preference a complex with a metal selected from Ag, Al, Ce, Co, Cu, Fe, Mo, Mn, Ni, Pb, Re, Ti, V, and Zn in any oxidation states, the metal being selected by preference from Co(II), Co(III), Cu(I), Cu(II), Fe(II), Fe(III), Mn(II), Mn(III), Ni(II), Pb(II), and Zn(II), particularly preferably from Mn(II) and Mn(III).
The metal-ligand complex can, as a rule be manufactured easily by mixing a metal salt of the corresponding metal with the corresponding ligand in an aqueous environment. The production of a desired oxidation state can be favored by establishing a suitable redox potential.
Any counterion, in particular acetate, tetrafluoroborate, fluoride, bromide, iodide, or chloride, is suitable in principle for saturating the valences still unoccupied, and/or any charge that is still free, after binding to the ligand.
A further subject of the present invention is likewise the use of washing and cleaning agents according to the present invention for the cleaning of textile fabrics and for the cleaning of hard surfaces.
Also a subject of the present invention are the aforementioned ligands and metal-ligand complexes according to the present invention as such. The metal-ligand complexes according to the present invention are also hereinafter called “bleach catalysts according to the present invention.”
A particular subject of the present invention is metal-ligand complexes of ligands of the general formula (I), by preference of ligands of the general formula (II) or (II), in particular of ligands of the general formula (IV) or (V),
wherein in order to increase solubility, the skeleton of the ligand carries at least one residue encompassing at least one group selected from nitro, sulfato, sulfo, amidosulfo, hydroxycarbonyl, alkoxycarbonyl, aryloxycarbonyl, amidocarbonyl, phosphate, phosphono, amidophosphono, hydroxy, alkoxy, amino, polyoxyethylene, and halogen as substituents, wherein the residue can be selected in this context in particular from sulfo, sulfoalkyl, in particular sulfo-C1-18 alkyl, hydroxycarbonyl, hydroxycarbonylalkyl, in particular hydroxycarbonyl-C1-18 alkyl, phosphono, phosphonoalkyl, in particular phosphono-C1-18 alkyl, hydroxy, hydroxyalkyl, in particular hydroxy-C1-18 alkyl, amino, aminoalkyl, in particular amino-C1-18 alkyl, halogen, haloalkyl, in particular halo-C1-18 alkyl, —(CH2—CH2—O—)nH, and C1-18 alkyl-(CH2—CH2—O—)nH where in each case n=1 to 20, by preference 3 to 20.
A further particular subject of the present invention is metal-ligand complexes of ligands of the general formula (I), by preference of ligands of the general formula (II) or (III),
where at least one heterocycle, by preference all three heterocycles, are bicyclic heterocycles selected, in particular, from optionally substituted benzimidazole, benzoxazole, and benzothiazole.
A further particular subject of the present invention is metal-ligand complexes of ligands of the general formula (I), by preference of ligands of the general formula (II) or (III),
wherein the heterocycle is a 6-membered heterocycle, selected in particular from optionally substituted pyridine, pyrimidine, or pyrazine, and wherein the metal is selected from Mn(II) and Mn(III).
A further subject of the present invention is also the use of ligands and for metal-ligand complexes according to the present invention in washing or cleaning agents, in particular for the cleaning of textile fabrics and for the cleaning of hard surfaces.
A further subject of the present invention is also the use of ligands and/or metal-ligand complexes according to the present invention, in particular as adjuvants, for the cleaning of textile fabrics and for the cleaning of hard surfaces.
A further subject of the present invention is also the use of ligands and/or metal-ligand complexes according to the present invention for bleaching woodpulp and/or raw cotton.
The washing and cleaning agents according to the present invention can be all conceivable types of cleaning agent, both concentrates and agents to be used undiluted, for use on a commercial scale, in a washing machine or for hand laundering or cleaning. These include, for example, washing agents for textiles, carpets, or natural fibers, for which the term “washing agent” is used according to the present invention. These also include, for example, dishwashing agents for automatic dishwashers or manual dishwashing agents, or cleaners for hard surfaces such as metal, glass, porcelain, ceramic, tiles, stone, painted surfaces, plastics, wood, or leather; the term “cleaning agent” is used for these according to the present invention. In the wider sense, sterilization and disinfection agents are also to be regarded as washing and cleaning agents for purposes of the invention.
Embodiments of the present invention encompass all presentation forms established according to the existing art and/or all useful such forms of the washing or cleaning agents according to the present invention. These include, for example, solid, powdered, liquid, gelled, or pasty agents, optionally also made up of multiple phases, compressed or uncompressed; also included thereamong are extrudates, granules, tablets, or pouches, packaged both in large containers and in portions.
In a preferred embodiment, the washing or cleaning agents according to the present invention contain the above-described bleach catalysts according to the present invention in a quantity of up to 5 wt %, in particular from 0.001 wt % to 1 wt %, and particularly preferably from 0.01 wt % to 0.5 wt %, especially from 0.01 to 0.25 wt %, based in each case on the total weight of the washing or cleaning agent.
In addition to the bleach catalysts according to the present invention, other bleach catalysts can also be additionally contained, if applicable, in the agents according to the present invention. These substances can be, in general, any bleach-intensifying transition metal salt or any transition metal complex. Suitable transition metals in this context are, in particular, Mn, Fe, Co, Ru, Mo, Ti, V, or Cu, in different oxidation states. Suitable as possible complexing ligands are in particular, as described in the literature, guanidines, aminophenols, amine oxides, salenes, saldimines, lactams, monocyclic and cross-bridged polycyclic polyazaalkanes, terpyridines, dendrimers, tetraamido ligands, bis- and tetrakis(pyridylmethyl)alkylamines, secondary amines, and polyoxometallates.
In a preferred embodiment, a complex of manganese in oxidation state II, III, IV, or V, that by preference contains one or more macrocyclic ligands having the donor functions N, NR, PR, O, and/or S, is used as an additional bleach catalyst. Ligands that comprise nitrogen donor functions are used by preference in this context. It is particularly preferred in this context to use additionally in the agents according to the present invention a bleach catalyst that contains, as macromolecular ligands, 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me/Me-TACN) and/or 2-methyl-1,4,7-triazacyclononane (Me/TACN). Suitable manganese complexes are, for example, [MnIII2(μ-O)1(μ-OAc)2(TACN)2](ClO4)2, [MnIIIMnIV(μ-O)2(μ-OAc)1(TACN)2](BPh4)2, [MnIV4(μ-O)6(TACN)4](ClO4)4, [MnIII2(μ-O)1(μ-OAc)2(Me-TACN)2](ClO4)2, [MnIIIMnIV(μ-O)1(μ-OAc)2(Me-TACN)2](ClO4)3, [MnIV2(μ-O)3(Me-TACN)2](PF6)2, and [MnIV2(μ-O)3(Me/Me-TACN)2](PF6)2 (OAc═OC(O)CH3).
The additional bleach catalyst, if used, is also contained in the agents according to the present invention in a quantity of up to 5 wt %, in particular from 0.0025 wt % to 1 wt %, and particularly preferably from 0.01 wt % to 0.25 wt %, based in each case on the total weight of the washing or cleaning agent.
Also preferably contained in the washing and cleaning agents according to the present invention are bleaching agents, which by preference represent and/or supply the substrate for the bleach catalysts according to the present invention. A “bleaching agent” is to be understood in this context on the one hand as hydrogen peroxide itself and on the other hand as any compound that supplies hydrogen peroxide in an aqueous medium. Among the compounds yielding H2O2 in water and serving as bleaching agents, sodium percarbonate, sodium perborate tetrahydrate, and sodium perborate monohydrate are of particular importance. Other usable bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates, and peracid salts or peracids that yield H2O2, such as persulfates or persulfuric acid. Also usable is the urea peroxohydrate percarbamide, which can be described by the formula H2N—CO—NH2.H2O2. Especially when the agents are used for cleaning hard surfaces, for example in automatic dishwashing, they can if desired also contain bleaching agents from the group of the organic bleaching agents, although the use thereof is also possible, in principle, in agents for textile laundering. Typical organic bleaching agents are the diacyl peroxides such as, for example, dibenzoyl peroxide. Further typical organic bleaching agents are the peroxy acids; the alkylperoxy acids and arylperoxy acids are mentioned in particular as examples. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate; (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid (phthaloiminoperoxyhexanoic acid, PAP), o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid, and N-nonenylamidopersuccinates; and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-dioic acid, N,N-terephthaloyi-di(6-aminopercaproic) acid.
Substances that release chlorine or bromine can also be used as bleaching agents. Possibilities among the suitable materials releasing chlorine or bromine are, for example, heterocyclic N-bromamides and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid, and/or dichloroisocyanuric acid (DICA), and/or salts thereof with cations such as potassium and sodium. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydantoin, are likewise suitable.
In a particular embodiment according to the present invention, the use of substances that supply hydrogen peroxide is omitted, and oxygen is used instead as a bleaching agent; the oxygen can in this context be atmospheric oxygen, or oxygen that is released from an oxygen-supplying agent.
Washing or cleaning agents, in particular automatic dishwashing agents, that contain up to 45 wt %, in particular 1 to 35 wt %, by preference 2.5 to 30 wt %, particularly preferably 3.5 to 20 wt %, and in particular 5 to 15 wt % bleaching agent, by preference sodium percarbonate, are preferred according to the present invention.
The active oxygen content of the washing or cleaning agent, in particular of the automatic dishwashing agent, is by preference between 0.4 and 10 wt %, particularly preferably between 0.5 and 8 wt %, and in particular between 0.6 and 5 wt %, based in each case on the total weight of the agent. Particularly preferred agents have an active oxygen content above 0.3 wt %, preferably above 0.7 wt %, particularly preferably above 0.8 wt %, and in particular above 1.0 wt %.
Alternatively to and simultaneously with the bleaching agents, enzymes that, on the basis of other substrates, are capable of generating hydrogen peroxide in situ can also be used to make hydrogen peroxide available. This relates to oxidoreductases, which can transfer electrons from (as a rule) an organic substrate, for example glucose, to oxygen as an electron acceptor, and thus enable the formation in situ of the desired hydrogen peroxide. The oxidoreductase can be used in this context together with the corresponding organic substrate. Because the stains to be treated may already contain the necessary substrate, however, the oxidoreductases can be used, if applicable, even without addition of the corresponding substrate.
The oxidoreductase that generates hydrogen peroxide is by preference an oxidoreductase that produces hydrogen peroxide by using oxygen as an electron acceptor. Suitable in this context, in particular, are oxidoreductases of EC classes E.C. 1.1.3 (CH—OH as electron donor), E.C. 1.2.3 (aldehyde or oxo group as electron donor), E.C. 1.4.3 (CH—NH2 as donor), E.C. 1.7.3 (N-containing group as donor), and E.C. 1.8.3 (S-containing group as donor), enzymes of EC class E.C. 1.1.3 being preferred.
Preferred enzymes are selected, in particular, from the group made up of malate oxidase (EC 1.1.3.3), glucose oxidase (EC 1.1.3.4), hexose oxidase (EC 1.1.3.5), cholesterol oxidase (EC 1.1.3.6), galactose oxidase (EC 1.1.3.9), pyranose oxidase (EC 1.1.3.10), alcohol oxidase (EC 1.1.3.13), choline oxidase (EC 1.1.3.17, see esp. WO 04/58955), oxidases for long-chain alcohols (EC 1.1.3.20), glycerol-3-phosphate oxidase (EC 1.1.3.21), cellobiose oxidase (EC 1.1.3.25), nucleoside oxidase (EC 1.1.3.39), D-mannitol oxidase (EC 1.1.3.40), xylitol oxidase (EC 1.1.3.41), aldehyde oxidase (EC 1.2.3.1), pyruvate oxidase (EC 1.2.3.3), oxalate oxidase (EC 1.2.3.4), glyoxylate oxidase (EC 1.2.3.5), indole-3-acetaldehyde oxidase (EC 1.2.3.7), pyridoxal oxidase (EC 1.2.3.8), arylaldehyde oxidase (EC 1.2.3.9), retinal oxidase (EC 1.2.3.11), L-amino acid oxidase (EC 1.4.3.2), amine oxidase (EC 1.4.3.4, EC 1.4.3.6), L-glutamate oxidase (EC 1.4.3.11), L-lysine oxidase (EC 1.4.3.14), L-aspartate oxidase (EC 1.4.3.16), tryptophan-alpha, beta oxidase (EC 1.4.3.17), glycine oxidase EC 1.4.3.19), urea oxidase (EC 1.7.3.3), thiol oxidase (EC 1.8.3.2), glutathione oxidase (EC 1.8.3.3), sorbitol oxidase, and from enzymes such as those described in DE102005053529.
In a preferred embodiment, the hydrogen peroxide-producing oxidoreductase is one that uses a sugar as an electron donor. The hydrogen peroxide-producing and sugar-oxidizing oxidoreductase is by preference selected, according to the present invention, from glucose oxidase (EC 1.1.3.4), hexose oxidase (EC 1.1.3.5), galactose oxidase (EC 1.1.3.9), and pyranose oxidase (EC 1.1.3.10). Glucose oxidase (EC 1.1.3.4) is particularly preferred according to the present invention.
Advantageously, when a hydrogen peroxide-generating oxidoreductase is used, preferably organic, particularly preferably aromatic compounds interacting with the enzymes are additionally added in order to intensify the activity of the relevant oxidoreductases (enhancers) or, when the redox potentials between the oxidizing enzymes and the stains are very different, in order to ensure electron flow (mediators).
The hydrogen peroxide-producing oxidoreductase is utilized in the washing and cleaning agents according to the present invention, if it is used, by preference in a quantity such that the entire agent has an enzyme activity, based on the oxidoreductase, from 30 U/g to 20,000 U/g, in particular from 6 U/g to 15,000 U/g. The unit of 1 U (=unit) corresponds here to the activity of that quantity of enzyme that converts 1 μmol of its substrate at pH 7 and 25° C. in 1 minute.
The substrate to be used, if applicable, when a hydrogen peroxide-producing oxidoreductase of this kind is utilized is, as a rule, immediately apparent from the designation of the respective oxidoreductase.
Agents according to the present invention can also, if applicable, contain bleach activators as an additional bleaching adjuvant. Reference is made to Application WO 2008/125589 with regard to bleach activators preferably usable according to the present invention and the preferred utilization quantities thereof.
In addition to a bleach catalyst according to the present invention and the aforementioned bleaching agents and optionally contained further bleaching adjuvants, a washing or cleaning agent according to the present invention contains, if applicable, further ingredients such as further enzymes, enzyme stabilizers, surfactants, in particular nonionic, anionic, cationic, and/or amphoteric surfactants, detergency builders (builders, cobuilders), polymers, solvents, thickeners, sequestering agents, electrolytes, acidifying agents, optical brighteners, graying inhibitors, glass corrosion inhibitors, corrosion inhibitors, color transfer inhibitors, foam inhibitors, disintegration adjuvants, abrasives, dyes, fragrances, microbial active substances, UV absorbers, wrinkle-prevention agents, antistatic agents, so-called soil release active substances or soil repellents, propellants, and further usual ingredients as applicable.
With regard to further enzymes, enzyme stabilizers, surfactants, detergency builders, polymers, solvents, thickeners, sequestering agents, electrolytes, acidifying agents, optical brighteners, graying inhibitors, glass corrosion inhibitors, corrosion inhibitors, color transfer inhibitors, foam inhibitors, disintegration adjuvants, abrasives, dyes, fragrances, microbial active substances, UV absorbers, wrinkle-prevention agents, antistatic agents, soil release active substances, and propellants usable by preference according to the present invention, and to the preferred utilization quantities thereof, reference is made to Application WO 2008/125589.
Those bleach catalyst granules that contain, based on the total weight of the granule,

    
    
        a) 0.1 to 30 wt % of a bleach catalyst according to the present invention as well as, if applicable, further bleach catalyst,
        b) 10 to 99 wt % of a carrier material, and
        c) 0.1 to 5 wt % of a binding agent from the group of the organic polymers, have proven to be particularly advantageous.
    
    


The further bleach catalyst according to a) that is to be used as applicable is by preference selected from the further bleach catalysts already recited previously.
Suitable as carrier material b) are, in principle, all substances or substance mixtures, in particular the detergency builders already listed previously, especially the carbonates including the hydrogencarbonates, the sulfates, the chlorides, the silicates, and the phosphates, that are usable in washing and cleaning agents and compatible with the other ingredients. Particularly suitable in this context as a carrier material are alkali metal carbonate, alkali metal hydrogencarbonates, alkali metal sequicarbonates, alkali silicates, alkali metasilicates, alkali phosphates, and mixtures of said substances, wherein the alkali carbonates, in particular sodium carbonate, sodium hydrogencarbonate or sodium sesquicarbonate, and/or alkali phosphates, are used preferably for purposes of this invention. In a particularly preferred embodiment, pentasodium triphosphate, Na5P3O10 (sodium tripolyphosphate) or the corresponding potassium salt pentapotassium triphosphate, K5P3O10 (potassium tripolyphosphate) is used as a carrier material.
The weight proportion of carrier material b) in terms of the total weight of the bleach catalyst granules can be varied within the limits indicated above; in terms of processability and actual bleach performance after preparation with further ingredients having washing and cleaning activity, weight proportions above 20 wt %, by preference above 40 wt %, and in particular above 60 wt % have proven, in particular, to be advantageous. Bleach catalyst granules in which the weight proportion of carrier material b) in terms of the total weight of the granule is equal to 20 to 99 wt %, by preference between 40 and 95 wt %, and in particular between 60 and 90 wt %, are consequently preferred in the context of the present Application.
As a third ingredient, the bleach activator granules according to the present invention contain a binding agent c) from the group of the organic polymers. The polymers can be nonionic, anionic, cationic, or amphoteric in nature. Natural polymers and modified polymers of natural origin are usable, as are synthetic polymers.
The group of nonionic polymers used with particular preference as binding agent c) includes polyvinyl alcohols, acetalized polyvinyl alcohols, polyvinylpyrrolidones, and polyalkylene glycols, in particular polyethylene oxides. Preferred polyvinyl alcohols and acetalized polyvinyl alcohols have molecular weights in the range from 10,000 to 100,000 gmol−1, by preference from 11,000 to 90,000 gmol−1, particularly preferably from 12,000 to 80,000 gmol1, and in particular from 13,000 to 70,000 gmol−1. Preferred polyethylene oxides have molar weights in the range from approx. 200 to 5,000,000 g/mol, corresponding to degrees of polymerization n from approx. 5 to >100,000.
Members of the group of anionic polymers used with particular preference as binding agent c) are, in particular, homo- or copolymeric polycarboxylates, polyacrylic acids, and polymethyacrylic acids, in particular those that have already been recited previously as organic builder substances usable for washing and cleaning agents, as well as sulfonic acid group-containing polymers, in particular those that have already been recited previously as usable softeners.
With regard to the group of cationic and amphoteric polymers used with particular preference as binding agent c), reference is made to the polymers already listed previously as polymers having washing and cleaning activity.
In bleach catalyst granules preferred according to the present invention, the weight proportion of binding agent c) in terms of the total weight of the granule is between 0.2 and 4.5 wt %, preferably between 0.5 and 4.0 wt %, and in particular between 1.0 and 4.0 wt %.
The bleach catalyst granules preferably possess an average particle size between 0.1 and 1.0 mm, particularly preferably between 0.2 and 0.8 mm, and in particular between 0.3 and 0.7 mm, wherein the weight proportion of particles having a particle size less than 0.1 mm is by preference at least 4 wt %, particularly preferably at least 6 wt %, and in particular at least 8 wt %, but at the same time by preference at most 80 wt %, particularly preferably at most 60 wt %, and in particular at most 40 wt %, and the weight proportion of particles having a particle size between 0.2 and 0.8 mm is by preference between 30 and 70 wt %, particularly preferably between 45 and 65 wt %, and in particular between 40 and 60 wt %.
In addition to the bleach catalyst, it is also possible for enzymes or other (in particular, sensitive) ingredients to be prepared in the manner described above.
A separate subject of the invention is represented by methods for cleaning textiles or hard surfaces in which a bleach catalyst according to the present invention is used at least in one of the method steps.
Included thereamong are both manual and automatic methods. Embodiments are represented by, for example, hand laundering, manual removal of spots from textiles or from hard surfaces, or utilization in connection with an automatic method, wherein automatic methods are preferred, in particular for the cleaning of textiles, because of their more precise controllability with regard, for example, to contact times and quantities used. The concentration ranges referred to above apply in correspondingly preferred fashion to these applications.
The cleaning of textile fabrics is accomplished by preference at temperatures from 20 to 95° C., in a preferred embodiment at temperatures from 20 to 60° C., in particular at temperatures from 20 to 40° C., and by preference at a pH from 5 to 12, in particular from 8 to 11.
Methods for cleaning textiles are generally notable for the fact that, in multiple method steps, different substances having cleaning activity are applied onto the material to be cleaned and are washed off after the contact times or that the material to be cleaned is treated in another manner with a washing agent or with a solution of said agent. The same applies to methods for cleaning all materials other than textiles, which are grouped under the term “hard surfaces.” All conceivable washing or cleaning methods can be enriched, in at least one of the method steps, with a bleach catalyst according to the present invention, and then represent embodiments of the present invention.
In a preferred embodiment of this use, the bleach catalysts according to the present invention are made available in the context of one of the formulations set forth above for agents according to the present invention, by preference washing or cleaning agents, respectively.
A further subject of the present invention is also a product containing a composition according to the present invention or a washing or cleaning agent according to the present invention, in particular a cleaner according to the present invention for hard surfaces, and a spray dispenser. The product can in this context be both a single-chamber and a multi-chamber vessel, in particular a two-chamber vessel. In this context, the spray dispenser is preferably a manually activated spray dispenser, selected in particular from the group encompassing aerosol spray dispensers (pressurized-gas containers, also referred to inter alia as a spray can), spray dispensers that themselves build up pressure, pump spray dispensers, and trigger spray dispensers, in particular pump spray dispensers and trigger spray dispensers having a container made of transparent polyethylene or polyethylene terephthalate. Spray dispensers are described more exhaustively in WO 96/04940 (Procter & Gamble) and in the U.S. patents cited therein regarding spray dispensers, to which patents in their entirety reference is made in this regard, and the content of which is hereby incorporated into this Application. Trigger spray dispensers and pump atomizers possess the advantage, as compared with pressurized-gas containers, that no propellant needs to be used. By means of suitable particle-capable attachments, nozzles, etc, (so-called “nozzle valves”) on the spray dispenser, in this embodiment an enzyme that may be contained can optionally also be added to the agent in a form immobilized on particles, and thus metered as a cleaning foam.
Automatic dishwashing agents particularly preferred according to the present invention encompass 5 to 70 wt %, by preference 10 to 60 wt %, and in particular 20 to 50 wt % detergency builder(s) with the exception of polymers having washing and cleaning activity;

    
    
        2 to 28 wt %, by preference 4 to 20 wt %, and in particular 6 to 15 wt % polymers having washing and cleaning activity;
        0.5 to 10 wt %, by preference 1 to 8 wt %, and in particular 2 to 6 wt % surfactant(s), by preference nonionic and/or amphoteric surfactant(s);
        0.5 to 8 wt %, by preference 1 to 7 wt %, and in particular 2 to 6 wt % enzyme(s);
        2 to 20 wt %, by preference 4 to 15 wt %, and in particular 6 to 12 wt % bleaching agent;
        0.01 to 5 wt %, by preference 0.02 to 4 wt %, and in particular 0.05 to 3 wt % bleach catalysts according to the present invention; and, if applicable,
        0.01 to 5 wt %, by preference 0.02 to 4 wt %, and in particular 0.05 to 3 wt % further bleach catalysts.
    
    


Very particularly preferred automatic dishwashing agents encompass

    
    
        5 to 70 wt %, by preference 10 to 60 wt %, and in particular 20 to 50 wt % phosphates;
        2 to 28 wt %, by preference 4 to 20 wt %, and in particular 6 to 15 wt % polymers having washing and cleaning activity;
        0.5 to 10 wt %, by preference 1 to 8 wt %, and in particular 2 to 6 wt % nonionic surfactant(s);
        0.5 to 8 wt %, by preference 1 to 7 wt %, and in particular 2 to 6 wt % enzyme(s) selected from amylases, proteases, and amadoriases;
        2 to 20 wt %, by preference 4 to 15 wt %, and in particular 6 to 12 wt % percarbonate;
        0.01 to 5 wt %, by preference 0.02 to 4 wt %, and in particular 0.05 to 3 wt % bleach catalysts according to the present invention; and, if applicable,
        0.01 to 5 wt %, by preference 0.02 to 4 wt %, and in particular 0.05 to 3 wt % further bleach catalysts.
    
    


Automatic dishwashing agents according to the present invention can be prepared in various ways. The agents according to the present invention can be present in solid or liquid presentation forms, and as a combination of solid and liquid presentation forms.
Powders, granules, extrudates, or compactates, in particular tablets, are suitable in particular as solid presentation forms. The liquid presentation forms based on water and/or organic solvents, can be present in thickened fashion in the form of gels.
Agents according to the present invention can be prepared in the form of single-phase or multi-phase products. Automatic dishwashing agents having one, two, three, or four phases are particularly preferred. Automatic dishwashing agents, present in the form of a prefabricated dispensing unit having two or more phases, are particularly preferred.
The individual phases of multi-phase agents can have the same or different aggregate states. Automatic dishwashing agents that comprise at least two different solid phases and/or at least two liquid phases and/or at least one solid and at least one solid phase are preferred in particular.
Automatic dishwashing agents according to the present invention are preferably pre-packaged into dispensing units. These dispensing units preferably encompass the quantity of substances having washing or cleaning activity that is necessary for one cleaning cycle. Preferred dispensing units have a weight between 12 and 30 g, preferably between 14 and 26 g, and in particular between 16 and 22 g.
With particular preference, the volume of the aforesaid dispensing units, and their three-dimensional shape, are selected so that dispensability of the pre-packaged units via the dispensing chamber of an automatic dishwasher is guaranteed. The volume of the dispensing unit is therefore preferably between 10 and 35 ml, by preference between 12 and 30 ml, and in particular between 15 and 25 ml.
The automatic dishwashing agents according to the present invention, in particular the prefabricated dispensing agents, particularly preferably possess a water-soluble casing.
The Examples that follow describe the invention further without limiting it thereto.
EXEMPLIFYING EMBODIMENTS
Example 1
Preparation of the timp Ligands Used
General:




Preparation is based on the corresponding N-methylimidazoles, for 1-methylimidazole, 1,4,5-trimethylimidazole, and 1-methylbenzimidazole.
The corresponding imidazole is first reacted with n-BuLi at −78° C. in THF or dibutyl ether, and thereby deprotonated/lithiated at the most acidic location (the C2 carbon atom). The reaction proceeds quickly, and is complete after about 30 minutes.
The resulting lithiated imidazole can then be quenched at low temperature (−78° C. to −40°) with 0.33 eq PCl3 in order to obtain the desired tris(imidazol-2-yl)phosphine.
Both the use of PBr3 instead of PCl3, and an inverse reaction procedure (adding the lithiated imidazole to a precooled solution of PBr3 in THF), result in a definite increase in yield.
The use of THF as a solvent offers the advantage that the resulting salt load (LiBr) remains in solution, while the resulting tris(imidazol-2-yl)phosphine is generally very poorly soluble in THF and can thus be separated out by filtration. After subsequent removal of the solvent and redissolution of the remaining residue from ethanol and/or washing with an ethanol/acetone mixture (≈1:10), the products are obtained very cleanly with moderate to good yields. It is very highly recommended also to work under inert gas during preparation, since the products are slowly converted into the corresponding phosphine oxides by atmospheric oxygen.
Tris(1-methylimidazol-2-yl)phosphine (timp)
4.2 g (51 mmol) 1-methylimidazole is dissolved in 150 ml THF and cooled to −78° C. This is followed by rapid addition of 32 ml n-BuLi (1.6 M solution in hexane, 51 mmol). The resulting yellow solution is stirred for 30 min and then slowly (approx. 30 min) dripped into a solution, precooled to −78° C., of 4.6 g (17 mmol) PBr3 in 100 ml THF. The formation of an almost colorless solid is immediately observed. The resulting suspension is slowly warmed to room temperature (overnight), and the solid is filtered off and washed in an ultrasonic bath with an ethanol/acetone mixture (≈1:10).
The product is obtained as a colorless powder.
Yield: 4.67 g (77% of theoretical, based on PBr3)

    
    
        1H-NMR (300 MHz, DMSO-d6): δ=3.50 (s, 9H), 7.03 (s, 3H), 7.41 (s, 3H) ppm
        13C-NMR (75.5 MHz, DMSO-d6): δ=33.8, 125.7, 129.7 (d, 8.67 Hz), 140.0 (d, 12.14 Hz) ppm.
        31P-NMR (81 MHz): δ=−60 ppm.
    
    


Tris(1,4,5-trimethylimidazol-2-yl)phosphine (ttmimp)
4.49 g (40 mmol) 1,4,5-trimethylimidazole is dissolved in 150 ml THF and cooled to −78° C. This is followed by rapid addition of 25 ml n-BuLi (1.6 M solution in hexane, 40 mmol). The resulting yellow solution is stirred for 30 min and then slowly (approx. 30 min) dripped into a solution, precooled to −78° C., of 3.5 g (13 mmol) PBr3 in 100 ml THF. The formation of an almost colorless solid is immediately observed. The resulting suspension is slowly warmed to room temperature (overnight), and the solid is filtered off and washed in an ultrasonic bath with an ethanol/acetone mixture (≈1:10).
The product is obtained as a colorless powder.
Yield: 3.40 g (73% of theoretical, based on PBr3)

    
    
        1H-NMR (300 MHz, DMSO-d6): δ=2.02 (s, 9H), 2.06 (s, 9H), 3.39 (s, 9H) ppm
        13C-NMR (75.5 MHz, DMSO-d6): δ=8.6, 12.7, 31.7, 127.2, 134.5 (d, 8.09 Hz), 137.3 (d, 15.61 Hz) ppm.
        31P-NMR (81 MHz): δ=−112 ppm.
    
    


Tris(1-methylbenzimidazol-2-yl)phosphine (tbimp)
6.6 g (50 mmol) 1-methylimidazole is dissolved in 150 ml THF and cooled to −78° C. This is followed by rapid addition of 32 ml n-BuLi (1.6 M solution in hexane, 51 mmol). The resulting yellow solution is stirred for 30 min and then slowly (approx. 30 min) dripped into a solution, precooled to −78° C., of 4.5 g (16 mmol) PBr3 in 100 ml THF. The formation of an almost colorless solid is immediately observed. The resulting suspension is slowly warmed to room temperature (overnight), and the solid is filtered off and washed in an ultrasonic bath with an ethanol/acetone mixture (≈1:10).
The product is obtained as a colorless, flaky powder.
Yield: 1.83 g (27% of theoretical, based on PBr3)
31P-NMR (81 MHz): δ=−47 ppm.
Example 2
Preparation of the timp complexes used: [Mn(timp)2](X−)2




The complexes are prepared by reacting the corresponding tris(imidazol-2-yl)phosphine with 0.5 eq of a Mn(II) salt with preferably a weakly coordinating anion (BF4−), OAc−). If MnCl2 is used, for example, this results in only a 50% yield as compared with the corresponding complex with the tetrachloromanganate ion.
[Mn(timp)2(X−)2 and [Mn(ttmimp)2(X−)2:
2 mmol timp or ttmimp is weighed with 1 mmol MnX2, combined with 30 ml ethanol or acetonitrile, and heated in reflux for 2 hours. Water (≈1 ml) is added to the resulting suspension while hot, until the solid has gone completely into solution. Upon slow cooling to room temperature, the complex occurs quantitatively as a colorless, crystalline solid.
[Mn(timp)2](BF4−)2:










ESI-MS:




















m/z =
301.7
100%
[Mn(timp)2]2+




690.0
 18%
[Mn(timp)2]BF4+










IR (KBr): 3420, 3112, 2917, 2849, 1631, 1518, 1467, 1412, 1369, 1336, 1287, 1139, 1062, 944, 775, 757, 693, 506, 492, 416, 405 cm−1.

Crystal structure: SK—20

[Mn(ttmimp)2](BF4−)2










ESI-MS:




















m/z =
386
 73%
[Mn(ttmimp)2]2+




858
100%
[Mn(ttmimp)2]BF4+










IR (KBr): 3431, 2927, 1592, 1467, 1445, 1403, 1391, 1293, 1206, 1061, 787, 728, 585, 532, 466 cm−1.

Crystal structure: JDK67

[Mn(tbimp)2(X−)2:

2 mmol tbimp is weighed with 1 mmol MnX2, combined with 30 ml ethanol or acetonitrile, and heated in reflux for 2 hours. Water (≈1 ml) is added to the resulting suspension while hot, until the solid has gone completely into solution. Upon slow cooling to room temperature, the complex occurs quantitatively as a light-yellow, crystalline solid.
[Mn(ttmimp)2](BF4−)2:










ESI-MS:




















m/z =
451.8
100%
[Mn(tbimp)2]2+




990.0
 25%
[Mn(tbimp)2]BF4+










IR (KBr): 3428, 3055, 2951, 1611, 15891448, 1409, 1374, 1328, 1283, 1244, 1158, 1054, 919, 812, 743, 690, 609, 582, 553, 537, 520, 414 cm−1.

Crystal structure: JDK60

Example 3
Preparation of tris(pyridin-2-yl)phosphine
In a 2-liter double-neck round bottom flask having a stopcock and two dropping funnels with gas equalization, a solution of 86 ml n-butyllithium (215 mmol, 2.5 M in hexane) and 350 ml diethyl ether is precooled to −100° C., and then a solution of 34 g 2-bromopyridine (215 mmol) in 150 ml diethyl ether is dripped in within 30 min at −100° C. The resulting deep-red solution is then stirred for at least a further 3 h at −100° C. before slowly adding (8 h, 10 mmol/h) a solution of 9.76 g PCl3 (71 mmol) in 150 diethyl ether. Once addition is complete, the reaction mixture is slowly warmed to room temperature (overnight). The resulting suspension of a colorless solid in brown solution is extracted twice with 100 ml 2M H2SO4, the combined aqueous phases are neutralized (pH≈7.5) with NaOH solution (50% in water), and the solid that forms is separated out and washed with a little water. After recrystallization twice from ethanol (−30° C.), the product is recovered in crystalline fashion as colorless needles.
Yield: 8.59 g (45% based on PCl3)
1H-NMR (300 MHz, CDCl3):
δ=7.19 (dtt 1H, J=6.2 Hz, J=1.3 Hz, J=1.1 Hz), 7.37 (tdd, 1H, J=7.7 Hz, J=4.2 Hz, J=2.1 Hz,), 7.59 (tt, 1H, J=7.74 Hz, J=2.0 Hz), 8.63 (d, 1H, J=4.5 Hz) ppm.
13C-NMR (75 MHz, CDCl3):
δ=122.8 (C3), 129.2 (C5), 135.8 (C4), 150.2 (C6), 161.6 (C2q) ppm.
31P-NMR (75 MHz, CDCl3):
δ=−0.8 ppm.
[Mn(tPyp)2](X−)2:
2 mmol tpyp is weighed with 1 mmol MnX2, combined with 30 ml ethanol and heated in reflux. Water or acetonitrile (≈2-3 ml) is added to the resulting suspension while hot, until the solid has gone completely into solution. Upon slow cooling to room temperature, the complex occurs quantitatively as a colorless, crystalline solid.
IR (KBr): 3635, 3553, 3066, 1624, 1582, 1460, 1426, 1282, 1237, 1167, 1049, 1008, 791, 767, 747, 711, 638, 508, 495, 430, 419 cm−1.
Example 4
Test of the Mn-timp Complex for Damage and Primary Washing Performance in the Miniaturized Washing Test
R═H, R1═H (htimp)
R=Me, R1═H (timp)
R=Me, R1=Me (ttmimp)
R=Me, R1═—(CH)4— (tbimp)
X═Cl, BF4 or acetate
The primary washing power and wet breaking load loss were tested in a miniaturized washing test, working with a complete liquid laundry detergent formulation. The pH values in the liquid formulation were adjusted with NaOH so that for a dispensing rate of 4.4 g/l and after addition of the other additives, the respective pH existed in the washing formulation. 4.4 μl liquid laundry detergent, 0.35 g/l H2O2, and 6.4 mg/l Mn-timp were added to water at 16° dH. The cavities of the sample container were each filled with 10 ml of the washing liquor.
For primary washing performance, a cotton substrate having the respective stain was clamped in the sample container and the container was rotated in the microwave for 1 h at the indicated temperature so that the liquid in the cavities was constantly in contact with the cotton. The treated fabric substrate was rinsed under running lukewarm water and then dried and color-measured.
For wet breaking load loss, a cotton strip of defined width (number of threads) was placed into each cavity of the sample container, and the container was rotated in the microwave for 1 h at 60° C. This treatment was repeated 20 times. The strips were then dried and dipped into a wetting solution before being torn with a tensile testing machine at a constant test speed. The tearing force of the treated cotton was compared with the tearing force of the untreated cotton, and the wet breaking load loss was calculated as a percentage.
Five determinations were made for primary washing power and for wet breaking load loss. The results for Mn-timp are presented below.







TABLE 1







Experimental results for Mn-timp















Wet



Primary washing
Primary washing
Primary washing
break-



power (Y value)
power (Y value)
power (Y value)
ing load


pH
BC1, T = 30° C.
BC3, T = 30° C.
BC1, T = 60° C.
loss [%]














7
49.2
49.2
49.3
9


8
50
50.1
51.9
3


9
50.1
50.4
52.4
4


10
50.7
51.5
54.3
6


11
52.6
55.1
59
8









For comparison, the results for the bleach catalyst Mn-TACN are presented below.








TABLE 2







Experimental results for Mn-TACN















Wet



Primary washing
Primary washing
Primary washing
break-



power (Y value)
power (Y value)
power (Y value)
ing load


pH
BC1, T = 30° C.
BC3, T = 30° C.
BC1, T = 60° C.
loss [%]














7
50.4
48.4
n.d.
20


8
52.0
51.3
n.d.
31


9
53.8
54.4
n.d.
33


10
57.0
56.2
n.d.
57


11
60.3
58.5
n.d.
83









It is evident that the primary washing power of the Mn-timp complex at 30° C. at the various pH values tested is weaker overall than that of Mn-TACN, but its value is still acceptable. The great advantage as compared with Mn-TACN is that the wet breaking load loss with the use of Mn-timp is much less than when Mn-TACN is used, so that the overall quotient between washing power and damage is much better for Mn-timp than for Mn-TACN.
Example 5
Washing Tests in a Model Washing Facility
The washing test is carried out in a temperature-controllable multi-agitator apparatus.
The test vessels used are 1-liter beakers in which an apparatus is present for mechanically stirring the washing bath. The stirring mechanism is designed so that on the one hand all the beakers are stirred at the same speed, and on the other hand the stirring direction periodically changes.
The washing chambers are loaded with approx. 16 g of ballast laundry and approx. 6 g of stained fabric (the fabric pieces are cut into a square shape approx. 6 cm on a side and are made of cotton). All the test fabrics are manufactured by CFT B.V. (Netherlands).
The stained fabrics involve the following bleach-relevant test substrates:
















CS-103
red wine



CS-3
red wine, aged



BC-1
tea



BC-3
tea



CS-15
bilberry juice










From these five test fabrics, a set of eight stained fabric pieces was assembled for the tests. This means that three stains are represented twice in the test.

In order to ascertain bleaching performance, the tristimulus value Y (brightness value) of the bleached fabric was determined, and was compared with the reference samples. The tristimulus value Y is calculated from the measured L value using the following mathematical relationship:

L=116(Y/Yn)1/3−16.

Measurement of the L values is carried out using a Minolta CM-508d spectrophotometer. Two basic scenarios are utilized for washing tests in order to determine bleaching activity: on the one hand, washing tests using a complete laundry detergent formulation without TAED (washing test with complete laundry detergent without TAED), and on the other hand a simplified washing test that contains only hydrogen peroxide and surfactants (H2O2 test). The following test parameters are used for the washing testing with a complete laundry detergent without TAED:

    
    
        Volume of laundry detergent solution: 750 ml
        Quantity of laundry detergent with TAED: (100 g CLD per 16 l of bath, hence 4.69 g per 750 ml)
        Quantity of laundry detergent without TAED: 4.55 g per 750 ml
        Metal catalyst: 0.0086 mmol per transition metal atom
        Temperature: 30° C.
        Washing time: 60 min
        Rinse volume: 500 ml
        Rinsing time: 15
        Water quality: artificially hardened deionized water with
        
            CaCl2×2 H2O (8.73 g per 25 l) and
            MgCl2×6 H2O (2.42 g per 25 l)=16° dH)
            pH 10.5 (carbonate buffer solution).
        
        
    
    


The washing results for the various transition metal complexes in a complete laundry detergent without TAED are shown in the table below. The value for a complete laundry detergent without TAED and without transition metal complexes (“no catalyst”), and the value for a complete laundry detergent with TAED, are shown as comparison values.







TABLE 3





Washing tests using complete laundry detergent without TAED


















Mn-timp
76



Co-timp
76



Fe-timp
71



Mn-ttmimp
73



Co-ttmimp
72



Fe-ttmimp
70



Mn-tbimp
73



Mn-htimp
74



Mn-tpyp
74



no catalyst
71.7



TAED
75.8










The following test parameters are used in the simplified washing test (H2O2 test):

    
    
        Volume of laundry detergent solution: 750 ml
        Quantity of H2O2: 10 mmol per liter
        Surfactants: LAS=0.58 g; LT07=0.12 g
        Metal catalyst: 0.0086 mmol per transition metal atom
        Temperature: 30° C.
        Washing time: 60 min
        Water quality: deionized water
        pH: 10.5 (carbonate buffer solution)
    
    


The washing results for the various transition metal complexes according to the simplified washing test (H2O2 test) are shown in the table below:







TABLE 4





Simplified washing test (H2O2 test)


















Mn-timp
76



Co-timp
76



Fe-timp
70



Mn-ttmimp
75



Co-ttmimp
76



Fe-ttmimp
76



Mn-tbimp
75



Mn-htimp
75



Mn-tpyp
76

## Claims

1. An agent for washing or cleaning a textile fabric, the agent comprising a surfactant selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant, and mixtures thereof; and at least one component selected from the group consisting of ligands of the general formula (I), ligand-metal complexes of ligands of the general formula (I), and combinations thereof:


X[-Het]3  (I)

wherein X represents a moiety selected from the group consisting of N,N(+)—R1, P, P(+)—R1, P(O), B, B(−)—R1, C—R2, or Si—R2; each Het independently represents an optionally-substituted, nitrogen-containing heterocycle; and R1 and R2 each independently represents hydrogen or other substituent.

2. The agent according to claim 1, wherein at least one Het is bound to X in an alpha position with reference to a nitrogen atom in the nitrogen-containing heterocycle Het.

3. The agent according to claim 2, wherein the at least one component is selected from the group consisting of ligands of the general formula (II), ligand-metal complexes of ligands of the general formula (II), and combinations thereof:



wherein each




independently represents an optionally substituted nitrogen-containing heterocycle comprising a —C═N— group.

4. The agent according to claim 2, wherein the at least one component is selected from the group consisting of ligands of the general formula (III), ligand-metal complexes of ligands of the general formula (III), and combinations thereof:



wherein each




independently represents a heterocycle having an aromatically stabilized nitrogen anion.

5. The agent according to claim 1, wherein X represents a moiety selected from the group consisting of N, P, or P(O), and each Het independently represents a monocyclic 5- or 6-membered, or a bicyclic 9- or 10-membered, optionally-substituted, nitrogen-containing heterocycle, wherein at least one Het is bound to X in an alpha position with reference to a nitrogen atom in the nitrogen-containing heterocycle Het.

6. The agent according to claim 1, wherein the at least one component is selected from the group consisting of ligands of the general formula (IV), ligands of the general formula (V), ligand-metal complexes of ligands of the general formula (IV), ligand-metal complexes of ligands of the general formula (V), and combinations thereof:



wherein each R independently represents a hydrogen or an optionally substituted alkyl.

7. The agent according to claim 1, wherein the at least one component comprises at least one substituent selected from ammonium, nitro, sulfato, sulfo, amidosulfo, hydroxycarbonyl, alkoxycarbonyl, aryloxycarbonyl, amidocarbonyl, phosphato, phosphono, amidophosphono, hydroxy, alkoxy, amino, polyoxyethylene, and halogen moieties.

8. The agent according to claim 1, wherein the at least one component comprises a metal-ligand complex of ligands of the general formula (I) comprising a metal selected from the group consisting of Ag, Al, Ce, Co, Cu, Fe, Mo, Mn, Ni, Pb, Re, Ti, V, and Zn in any oxidation state.

9. A method comprising: (a) providing a textile fabric; and (b) contacting the textile fabric with an agent according to claim 1.

10. A method comprising: (a) providing a textile fabric; and (b) contacting the textile fabric with an agent according to claim 3.

11. A method comprising: (a) providing a textile fabric; and (b) contacting the textile fabric with an agent according to claim 4.

12. A metal-ligand complex of a ligand of the general formula (I):


X[-Het]3  (I)

wherein X represents a moiety selected from the group consisting of N,N(+)—R1, P, P(+)—R1, P(O), B, B(−)—R1, C—R2, or Si—R2; each Het independently represents an optionally-substituted, nitrogen-containing heterocycle; and R1 and R2 each independently represents hydrogen or other substituent;
wherein at least one Het comprises a 6-membered heterocycle; and wherein the metal of the metal-ligand complex is selected from the group consisting of Mn(II) and Mn(III).