Title of Invention

METHOD OF TREATING A TEXTILE

Abstract

METHOD OF TREATING A TEXTILE A method of treating a textile such as a laundry fabric is provided, in which the textile is contacted with an organic substance which forms a complex with a transition metal, whereby the complex catalyses bleaching of the textile by atmospheric oxygen after the treatment. The organic substance may be used in dry form, or in a liquor that is then dried, such as an aqueous spray-on fabric treatment fluid or a wash liquor for laundry cleaning, or a non-aqueous dry cleaning fluid or spray-on aerosol fluid. The method can confer cleaning benefits to the textile after the treatment. Also provided is a dry textile having an organic substance applied or deposited thereon, whereby bleaching by atmospheric oxygen is catalysed on the textile. To The Controller of Patents The Patent Office At Mumbai

Full Text

FORM-2 THE PATENTS ACT, 1970 (39 OF 1970) COMPLETE SPECIFICATION (See Section 10 ; rule 13) 1. TITLE OF INVENTION METHOD OF TREATING A TEXTILE HINDUSTAN LEVER LIMITED, a company incorporated under the Indian Companies Act. 1913 and having its registered office at Hindustan Lever house, 165/166, Backbay Reclamation, Mumbai -400 020, Maharashtra, India The following specification particularly describes the nature of the invention and the manner in which it is to be performed. This invention relates to a method of treating textiles such as laundry fabrics, more specifically to a method whereby bleaching by atmospheric oxygen is catalysed after the treatment. This invention also relates to textiles thus treated. In a conventional bleaching treatment, a substrate such as a laundry fabric or other textile is contacted is subjected to hydrogen peroxide, or to substances which can generate hydroperoxyl radicals, such as inorganic or organic peroxides. A preferred approach to generating hydroperoxyl bleach radicals is the use of inorganic peroxides coupled with organic precursor compounds. These systems are employed for many commercial laundry powders. For example, various European systems are based on tetraacetyl ethylenediamine (TAED) as the organic precursor coupled with sodium perborate or sodium percarbonate, whereas in the United States laundry bleach products are typically based on sodium nonanoyloxybenzenesulphonate (SNOBS) as the organic precursor coupled with sodium perborate. Alternatively, or additionally, hydrogen peroxide and peroxy systems can be activated by Dleach catalysts, such as by complexes of iron and the ligand N4Py (i.e. N, N-bis(pyridin-2-yl-mewyl)-bis(pyridin-2-yl)methylamine) disclosed in W095/34628, or the ligand Tpen (i.e. N, N, N\ N'-tetra(pyridin-2-yl-methyl)ethylenediamine) disclosed in W097/48787,^ It has long been thought desirable to be able to use atmospheric oxygen (air) as the source for a bleaching species, as this would avo.'d the need for costly fiydroperoxyl generating systems. Unfortunately, air-as such is kinetically inert towards bleaching substrates and exhibits no bleaching ability. Recently some progress has been made in this area. For example, WO 97/38074 reports the use of air for oxidising stains on fabrics by bubbling air througrfan aqueous solution containing an aldehyde and a radical initiator, whereas according to W095/34628 and W097/48787 referred to above, molecular oxygen may be used as the oxidant with the iron catalysts, as an alternative to peroxide generating systems. However, the known art teaches a bleaching effect only as long as fhe substrate is being subjected to the bleaching treatment. Thus, there is no expectation that hydrogen peroxide or peroxy bleach systems could continue to provide a bleaching effect on a treated substrate, such as a laundry fabric after washing and drying, since the bleaching species themselves or any activators necessary for the bleaching systems would be assumed to be removed from the substrate, or consumed or deactivated, on completing the wash cycle and drying. It would be desirable to be able to treat a textile such that, after the treatment is completed, a bleaching effect is observed on the textile. Furthermore, it would be desirable to be able to provide a bleach treatment for textiles such as laundry fabrics whereby residual bleaching occurs when the treated fabric has been treated and is dry. We have now found this can be achieved by a treatment method in accordance with the present invention, by catalysing bleaching of the substrate by atmospheric oxygen after treatment of the substrate. Accordingly, the present invention provides a method of treating a textile by contacting the textile with an organic substance which forms a complex with a transition metal, whereby the complex catalyses bleaching of the textile by atmospheric oxygen after the treatment. The present invention further provides a dry textile having an organic substance as defined above applied or deposited thereon, whereby bleaching by atmospheric oxygen is catalysed on the textile. Advantageously, by enabling a bleacliing effect even after the textile has been treated, the benefits of bleaching can be prolonged on the textile. Furthermore, since a bleaching effect is conferred to the textile after the treatment, the treatment itself, such as a laundry wash cycle, may for example be shortened. Moreover, since a bleaching effect is achieved by atmospheric oxygen after treatment of the textile, hydrogen peroxide or peroxy-baged bleach systems can be omitted from the treatment substance. The organic substance may be contacted to the textile fabric in any suitable manner. For example, it may be applied in dry form, such as in powder form, or in a liquor that is then dried, for example as an aqueous spray-on fabric treatment fluid or a wash liquor for laundry cleaning, or a non-aqueous dry cleaning fluid or spray-on aerosol fluid. Other suitable means of contacting the organic substance to the textile may be used, as further explained below. Any suitable textile that is susceptible to bleaching or one that one mighf wish to subject to bleaching may be used. Preferably the textile is a laundry fabric or garment. In a preferred embodiment, the method according 10 the present invention is carried out on a laundry fabric using an aqueous treatment liquor. In particular, the treatment may be effected in a wash cycle for cleaning laundry. More preferably, the treatment is carried out in an aqueous detergent bleach wash liquid. In a preferred embodiment, the treated textile is dried, by allowing it to dry under ambient temperature or at elevated temperatures. v The bleaching method may be carried out by simply leaving the substrate in contact with the organic substance for a sufficient period of time. Preferably, however, the organic substance is in an aqueous medium, and the aqueous medium on or containing the substrate is agitated. The organic substance can be contacted to the textile fabric in any conventional manner. For example it may be applied in dry form, such as in powder form, or in a liquor that is then dried, for example in an aqueous spray-on fabric treatment fluid or a wash liquor for laundry cleaning, or a non-aqueous diy cleaning fluid or spray-on aerosol fluid. In a preferred embodiment, the treated textile is dried, by allowing it to dry under ambient temperature or at elevated temperatures. In a particularly preferred embodiment the method according to the present invention is carried out" on a laundry fabric using aqueous treatment liquor. In particular the treatment may be effected in, or as an adjunct to, an essentially conventional wash cycle for cleaning laundry. More preferably, the treatment is carried out in an aqueous detergent wash liquor. The organic substance can be delivered into the wash liquor from a powder, granule, pellet, tablet, block, bar or other such solid form. The solid form can comprise a carrier, which can be particulate, sheet-like or comprise a three-dimensional object The carrier can be dispersible or soluble in the wash liquor or may remain substantially intact. In other embodiments, the organic substance can be delivered into the wash liquor from a paste, gel or liquid concentrate. It is particularly advantageous that the organic substance used in the method of the present invention makes use of atmospheric oxygen in its bleaching activity. This avoids the requirement that peroxygen bleaches and/or other relatively large quantities of reactive substances need be used in the treatment process. Consequently, only a relatively small quantity of bleach active substance need be employed and this allows dosage routes to be exploited which could previously not be used. Thus, while it is preferable to include the organic substance in a composition that is normally used in a washing process, such as a pre-treatment, main-wash, conditioning composition or ironing aid, other means for ensuring that the organic substance is present in the wash liquor may be envisaged. For example, it is envisaged that the organic substance can be presented in the form of a body from which it is slowly released during the whole or part of the laundry process. Such release can occur over the course of a single wash or over the course of a plurality of washes. In the latter case it is envisaged that he organic substance can be released from a carrier substrate used in association with the wash process, e.g. from a body placed in the dispenser drawer of a washing maciune, elsewhere in the delivery system or in the drum of the washing machine. When used in the drum of the washing machine the carrier can be freely moving or fixed relative to the drum. Such fixing can be • achieved by mechanical means, for example by ba. bs that interact with the drum-wall, or employ other forces, for example a magnetic force. The modification of a washing machine to provide for means to hold and retain such a carrier is envisaged similar means being known from the analogous art of toilet block manufacture. Freely moving carriers such as shuttles for dosage of surfactant materials and/or other detergent ingredients into the wash can comprise means for the release of the organic substance into the wash. In the alternative, the organic substance can be presented in the form of a wash additive that preferably is soluble. The additive can take any of the physical forms used for wash additives, including powder, granule, pellet, sheet, tablet, block, bar o: other such solid form or take the form of a paste, gel or liquid. Dosage of the additive can be unitary or in a quantity determined by the user. While it is envisaged that such additives can be used in the main washing cycle, the use of them in the conditioning or drying cycle is not hereby excluded. > The present invention is not limited to those circumstances in which a washing machine is employed, but can be applied where washing is performed in some alternative vessel. In these circumstances it is envisaged that the organic substance can be delivered by means of slow release from the bow), bucket or other vessel which is being employed, or from any implement which is being employed,,such as a brush, bat or dolly, or from any suitable applicator. Suitable pre-treatment means for application of the organic substance to the textile material prior to the main wash include sprays, pens, roller-ball devices, bars, soft solid applicator sticks and impregnated cloths or cloths containing microcapsules. Such means are well known in the analogous art of deodorant application and/or in spot treatment of textiles. Similar means for application are employed in those embodiments where the organic substance is applied after the main washing and/or conditioning steps have been performed, e.g. prior to or after ironing or drying of the cloth. For example, the organic substance may be applied using tapes, sheets or sticking plasters coated or impregnated with the substance, or containing microcapsules of the substance. The organic substance may for example be incorporated into a drier sheet so as to be activated or released during a tumble-drier cycle, or the substance can be provided in an impregnated or microcapsule-containing sheet so as to be delivered to the textile when ironed. The organic substance may comprise a preformed complex of a ligand and a transition metal. Alternatively, the organic substance may comprise a free ligand that complexes with a transition metal already present in the water or that complexes with a transition metal present in the substrate. The organic substance may also be included in the form of a composition of a free ligand or a transition metal-substitutable metal-ligand complex, and a source of transition metal, whereby the complex is formed in situ in the medium. The organic substance forms a complex with one or more transition metals, in the latter case for example as a dinuclear complex. Suitable transition metals include for example: manganese in oxidation states II-V, iron I-IV, copper I-I.U, cobalt I-III, nickel I-in, chromium II-VII, silver I-II, titanium II-IV, tungsten IV-VI, palladium II, ruthenium II-V, vanadium II-V and molybdenum Il-VI. In a preferred embodiment, the organic substance forms a complex of the general formula (A 1): [MaLkXn]Ym L represents a Hgand as herein defined, or its protonated or deprotonated analogue; 0 X represents a coordinating species selected from any mono, bi or tri cliarged anions and any "neutral molecules able to coordinate the metal in a mono, bi or tridentate manner, preferably selected from 02\ RB022*, RCOO', RCONR*, Oh", N03\ N02", NO, CO, S2\ RS\ P03***, STP-derived anions, P03OR-\ H20, C032", HC03\ ROH, NRRTT, RCN, Cl\ Br", OCN", SCN", CN\ N3", F, r, RO\ CIO/, S047\ HS04\ S032" and RS03\ and more preferably selected from 02\ RB022*, RCOO", OH", N03\ NO2", NO, CO, CN* , S2', RS", POA H20, C032\ HC03\ ROH, NRR'R", Cl*, Br*, OCN", SCN", RCN, N3o F, r, RO", CIO4', S042*, HS04", S032' and RS03* (preferably CF3S03"); Y represents any non-coordinated counter ion, preferably selected from CIO4*, .BR4*, [FeCU]", PF6*. RCOO*, N03", N02\ RO*, N*RR'R"R",1 Cl", Br", F, r, RSO3", S2062*, OCN*, SCNT, Li+, Ba2+, Na+, Mg2+, K+, Ca2\ Cs+, PR4+, RBO,2*, S042\ HS04*, SO32', SbCU", CuCU2*, CN, P043', HPO42", H2P04*. STP-derived anions, C032", HC03" and BF4\ bad more preferably selected from C104\ BR4", [FeCU]', PF6', RCOO", N03", N02*, RO*,h*+RR,R"Rm, Cl", Br*, F, I*, RS03* (preferably CF3S03"), S2062", OCN*, SCN*, Li+, Ba2+, Na+, Mg2+, K+, Ca2+, PR4+, S042", HS04", S032*, and BF4"; R, R*, R", R*" independently represent a group selected from hydrogen, hydroxyl, -OR (wherein R= alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl,.heteroaryl or carbonyl derivative group), -OAr, alky), alkenyl, cycloalkyl, heterocycloalkyl," aryl, heteroaryl and carbonyl derivative groups, each of R, Ar, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aiyl, heteroaryi and carbonyl derivative groups being optionally substituted by one or more functional groups E, or Kb together with R7 and independently R8 together with R9 represent oxygen, wherein E is selected from junctional groups containing oxygen, sulphur, phosphorus, nitrogen, selenium, halogens, and any electron donating and/or withdrawing groups, and preferably R, R', R", R"' represent hydrogen, optionally substituted alkyl or optionally substituted aryl, more preferably hydrogen or optionally substituted phenyl, naphthyl or Ci-4-alkyl; a represents an integer from I to 10, preferably from 1 to 4; k represents an integer from 1 to 10; n represents zero or an integer from 1 to 10, preferably from 1 to 4; m represents zero or an integer from 1 to 20, preferably from 1 to 8. Preferably, the ligand L is of the general formula (BI): wherein g represents zero or an integer from 1 to 6; r represents an integer from 1 to 6; s represents zero or an integer from 1 to 6; Zl and Z2independently represent a heteroatom or a heterocyclic or heteroardteiatic ring, Zl and/or 22 being optionally substituted by one or more functional groups E as defined below; Ql and Q2 independently represent a group of the formula: wherein if s>l, each -[-Zl(RlMOJ)rJ- group is independently defined; Rl, R2, R6, R7, R8, R9 independently represent a group selected from hydrogen, hydroxyl, -OR (wherein R= alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or carbonyl derivative group), -OAr, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and carbonyl derivative groups, each of R, Ar, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and carbonyl derivative groups being optionally substituted by one or more functional groups E, or R6 together with R7 and independently R8 together with R9 represent oxygen; E is selected from functional groups containing oxygen, sulphur, phosphorus, nitrogen, selenium, halogens, and any electron donating and/or withdrawing groups (preferably E is selected from hydroxy, mono- or polycarboxylate derivatives, aryl, heteroaryl, sulphonatc, thiol (-RSH), thioethers (-R-S-R*), disulphides (-RSSR'), dithiolenes, mono- or polyphosphonates, mono- or polyphosphates, electron donating groups and electron withdrawing groups, and groups of formulae (G')(G2)N-, (G')(G2) 0 (G3)N-, (G,)(G2)N-C(0>, G30- and G3C(OK wherein each of G1, G2 and G3 is independently selected from hydrogen, alkyl, electron donating groups and electron withdrawing groups (in addition to any amongst the foregoing)); or one of R1-R9 is a bridging group bound to another moiety of the same general formula; Tl and T2 independently represent groups 114 and R5, wherein R4 and R5 are as defined for R1-R9, and if g=0 and s>0, Rl together with R4, and/or R2 together with R5, may optionally independently represent =CH-i(.10, wherein RIO is as defined for Rl-R9,or Tl and T2 may together (-T2-T1-) represent a covalent bond linkage when s>l and g>0; if Zl and/or Z2 represent N aud Tl and T2 together represent a single bond linkage and Rl and/or R2 are absent, Ql and/or Q2 may independently represent a group of the formula: =CH-[-Y 1 ~]e-CH= , optionally any two or more of Rl, R2, R6, R7, R8, R9 independently are linked together by a covalent bond; if Zl and/or Z2 represents O, men Rl and/or R2 do not exist; c if Zl and/or Z2 represents S, N , P, B or Si then Rl and/or R2 may be absent; if Zl and/or 71 represents a heteroatom substituted by a functional group E then Rl and/or R2 and/or R4 and/or R5 may be absent. The groups Zl and 72 preferablylndependently represent an optionally substituted heteroatom selected fromN, P, 0, S, B and Si or anoptionally substituted heterocyclic ring or an optionally substituted heterbaromatic ring selected from pyridine, pyrimidines, pyrazine, pyramiding, pyrazole, pyrrole, imidazole, benzimidazole, quinoleine, isoquinoline, carbazole, indole, isoindole, furane, thiophene, oxazole and thiazole. \ The groups R1-R9 are preferably independently selected from -H, hydroxy-Co-Cao-alkyl* halo-Co-C2o-alkyl, nitroso, formyI-Co-C2o-alkyl, carboxyl-Co-C2o-alkyl and esters and salts thereof, carbamoyl-Co-C2o-alkyl, sulpho-Co-C2o-aIkyl and esters and salts thereof, sulphamoyl-C0-C20-alkyl, amine-Co-C2o-alkyl, aryl~Co-C2o-alkyl, heteroaryI-Co-C20-alkyl, Co-C2o-alkyl, alkoxy-Co-Cg-alkyl, carbonyl-Co-C6-alkoxy, and aryl-C One of R1-R9 may be a bridging group which limcr the ligand moiety to a second ligand moiety of preferably the same general structure. In this case the bridging group may have the formula bound between the two moieties, wherein p is zero or o^e, D is selected from a heteroatom or a heteroatom-containing group, or is part of an aromatic or saturated homonuclear and heteronuclear ring, n' is an integer from 1 to 4, m' is an integer from 1 to 4, with ths proviso that n'+m' In a first variant according to formula (BI), the groups Tl and T2 together form a single bond linkage and s>l, according to general formuia (BH): wherein Z3 independently represents a group as defined for Zl or 7.2; R3 independently represents a group as defined for R1-R9; Q3 independently represents a group as defined for Ql, Q2; h represents zero or an integer from 1 to 6; and s'=s-l. and more preferably selected from: In a first embodiment of the first variant, in general formula (BI1), s'=l, 2 or 3; r=g=h=l; d=2 or 3; e=f=0; R6=R7~H, preferably such that the ligand has a general formula selected frqm: In these preferred examples, Rl, R2, R3 and R4 are preferably independently selected from -H, alkyl, aryl, heteroaryl, and/or one of R1-R4 represents a bridging group bound to another moiety of the same general formula and/or two or more of Rl -R4 together represent a bridging group linking N atoms in the same moiety, with the bridging group being alkylene or hydroxy-alkylene or a heteroaryl-containing bridge, preferably heterojuyiene. More preferably, Rl, R2, R3 and R4 are independently selected from -H, methyl, emyl, isopropyl, nitrogen-containing hetercaryi. or a bridging group bound to another moiety of the same general formula or linking N atoms in the same moiety with the bridging group being alkylene or hydroxy-alkylene. According to this first embodiment, in the complex [Mat^XnJYn, preferably: M= MnOIHTV), Cu(D-(ni), Fe(n>-(in), Co(II>aU); X- CH3CN, OH2, CI", Br", OCN\ N3-, SCN\ 01+, O2", PO43-, C6H5B022-, RCOO-; Y= CIO/, BPh/, Br -, CI \ [FeCU]', PF6", NCV a=l,2,3,4; m= 1,2, 3,4; and k= 1,2,4. In a setori(i embodiment of the first variant, in general t'oj-muia (BIT), s'-2; r=g~h=\; d-f-0;e=i; and each Yl is independently alkylene or heteroaryiene> xhe ijgand preferably has the general formula: A4\ ^NrR2 R3 wherei^ A|, A2, A3, A4 are independently selected from C^_9-alkylene or heteroarylene groups^ and Ni and N2 independently represent a hetero atom or a heteroarylene group. In a preferred second embodiment, Nj represents an aliphatic nitrogen, N2 represents a heteroarylene group, Rl, R2, R3, R4 each independently represent -H, alkyl, aryl or heteroaryl, and A\, A2, Ai, A4 each represent -CH2-. One of R1-R4 may represent a bridging group bound to another moiety of the same genera] formula and/or two or more of R1-R4 may together represent a bridging group linking N atoms in the same moiety, with the bridging group being alkylene or hydroxy-alkylene or a heteroaryl^ontaining bridge. Preferably, R1.R2, R3 and R4 are independently selected from -H, methyl, ethyl, isopropyl, nitrogen-containing heteroaryl, or a bridging group bound to another moiety of the same general formula or linking N atoms in the same moiety with the bridging group being alkylene or hydroxy-alkylene. Particularly preferably, the ligand has the general formula: wherein Rl, R2 each independently represent -H, alkyl, aryl or heteroaryl. t \ i ' According to this second embodiment, in the complex [M8LkXn]Ym preferably: M= Fe(lI>(III), Mn(U)-(TV), Cu(II), Co(II)-(III); X= CH3CN, OH2, Cl\ Br', OCN\ N3", SCN\ OH', 02\ PO43*, C6H5BO22', RCOO"; Y= C10 a-1,2, 3,4; n= 0,1,2,3,4,5,6,7,8,9; m= 1,2, 3,4; and k= 1,2,4. In a third embodiment of the first v;iriant, in general formula (BII), s'=2 and r=g=h=l, according to the general formula: In this third embodiment, preferably each Z1-Z4 represents a heteroaromatic ring; e=f=0; d«l; and R7 is absent, with preferably R1=R2=R3=R4= 2,4,6-trimethyl-3-S03Na-phenyl, 2,6-diCl-3(or 4>SChNa-phenyi. Alternatively, each Z1-Z4 represents N; R1-R4 are absent; both Ql and Q3 represent =CH-[-Yl-]e-CH= ; and both Q2 and Q4 represent -CH2-[-Yl-]„-CH2-. Thus, preferably the ligand has the general formula: 17 wherein A represents optionally substituted alkyiene optionally interrupted by a hetcroatom; and n is zero or an integer from 1 to 5. Preferably, R1-R6 represent hydrogen, n=l and A= -CH2-, -CHOH-, -CH2N(R)CH2- or CH2CH2N(R)CH2CH2- wherein R represents hydrogen or alkyl, more preferably A" -CHr, -CHOH- or -CH2CH2NHCH2CH2-. According to this third embodiment in the complex [MaL|;Xn]Ym preferably: M= Mn(II)-OV), Co(D)-(III), Fe(ll>ail); X= CH3CN, OH2, CI\ Br\ OCN\ N3\ SCN*, OH\ O2-, PO Y= C104\ BPh/, Br", CI/, [FeCl4]*, PF6', NOV; a=l,2,3,4; n= 0,1,2,3,4,5,6,7,8,9; m= 1,2,3,4; and k-1,2,4. 1*3 U In a second variant according to formula (Bl), Tl and T2 independently represent groups R4, R5 as defined for R1-R9, according to the general formula (Bill): In a first embodiment of the second variant, in general formula (BUI), s= 1: r=l; g=0; d=f=l; e=J-4; Yl = -CH2-; and Rl together with R4, and/or R2 together with R5, independently represent =CH-R10, wherein RIO is as defined for Rl -R9. In one example, R2 together with R5 represents =CH-R10, with Rl and R4 being two separate groups. Alternatively, both Rl together with R4, and R2 together with R5 may independently represent =CH-R10. Thus, preferred ligands may for example have a Preferably, the ligand is selected from: / ^ _ /=N 0 N—R1 R2 R4-N I R3 N R1 wherein Rland R2 are selected from optionally substituted phenols, heteroaryl-Co-C2o-alkyls, R3 and R4 are selected from -H, alkyl, aryl, optionally substituted phenols, heteroaryl-C(rC2o-alkyls, alkylaryl, aminoalkyl, alkoxy, more preferably Rl and R2 being selected from optionally substituted phenols, heteroaryl-Co-Ca-alkyls, R3 and R4 are selected from -H, alkyl, aryl, optionally substituted phenols, nitrogen-heteroaryl-Co-C2-alkyls. According to this first embodiment, in the complex [M,LkX„]Ym preferably: M= Mn(IIMTV), Co(irxni), Fe(II)-(III); X= CH3CN, OHi, CI", Br", OOT, N3\ SCN*, OH*, &', PO43\ C^sBOj2", RCOO-; Y= CIO4", BPh/, Br', CI', [FeCL,]", PF6\ N03"; a= 1,2,3,4; n= 0,1,2,3,4,5,6,7,8,9; m= 1,2,3, 4; and k-1,2,4. In a second embodiment of the second variant, in general formula (Bill), s=l; r=l; g=0; d=f=l; e=l-4; Yl= -C^'XR"), wherein R' and R" are independently as defined for R1-R9. Preferably, the ligand has the general formula: The groups Rl, R2, R3, R4, R5 in this formula are preferably -H or Co-C;>o-aUcyJ, n=0 or 1, R6 is -H, alkyl, -OH or -SH, and R7, R8, R9, RIO are preferably each independently selected from -H, C0-G2o-alkyl, heteroaryl-C0-C2o-alkyl, alkoxy-Co-Cg-alkyl and amino* Co-C2o-alkyl. According to this second embodiment, in the complex [MaLtXnJYm preferably: M= Mn(II>(TV), Fe(IIMni), Cu(Ii), Co X= CH3CN, OH2, Cl\ Br\ OCN\ N3\ SCN\ OH", O2, P043\ C^BO:2', RCOO'; Y= CIO4", BPh/, Br \ CI \ [FeCU]\ PF6', NO3'; &- 1,2,3,4; n=0,1,2,3,4; m=0,1,2,3,4,5, 6, 7, 8; and k=l,2,3,4. More preferably, the ligand has the general formula: In a third embodiment of the second variant, in general formula (Bill), s=0; g=i; d= f=l-4. Preferably, the ligand has the general formula: R2 R3 wherein Rl, R2, R3 are as defined for R2, R4, R5. According to this third embodiment, in the complex [M.LtXn]Ym preferably: M= MnOIHIV), Fe(II>(in). Cu(II), Co(II)-(lfl); 21 X= CH3CN, 0H2, Cl*. Br', OCN-, N3', SOT, 0H\ 02\ PO43*, C^BC^2*, RCOO'; Y= C104\ BPh4\ Br\ Cl\ [FeCL,]', PF6\ N03'; a= 1,2,3,4; n= 0,1,2,3,4; m=0,1,2,3,4,5,6,7, 8; and k=l,2,3,4. In a fourth embodiment of the second variant, the organic substance forms a complex of the general formula (A): [LMXn]zYq in which M represents iron in the II, IH,IV or V oxidation state, manganese in the II, III, F/,0 VI or VII oxidation state, copper in the I, II or III oxidation state, cobalt in the n, HI or IV oxidation state, or chromium in the II-VI oxidation state; X represents a coordinating species; n represents zero or an integer in the range from 0 to 3; z represents the charge of the; complex and h an ir.tejger which can be positive, zero or negative; Y represents a counter ion, the type of which is dependent on the charge of the complex; qV= z/[charge Y]; and L represents a pentadentate ligand of the general formula (B): wherein each R1 , R2 independently represents -R4-tl5, R3 represents hydrogen, optionally substituted alkyl, aryl or aryla'.kyl, or -R4-Rs, each R4 independently represents a single bond or optionally substituted alkylene, alkenylene, oxyalkylene, aminoalkytene, alkylene ether, carhoxylic ester or carboxylic amide, and each R5 independently represents an optionally N-substituted aminoalkyl group or an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pjrimidinyl, triazolyl and thiazolyl. The ligand L having the general formula (B), as defined above, is a pentadentate ligand. By 'pentadentate' herein is meant that five hetero atoms can coordinate to the metal M ion in the metal-complex. In formula (B), one coordinating hetero atom is provided by the nitrogen atom in the methylamine backbone, and preferably one coordinating hetero atom is contained in each of the four R1 and R2 side groups. Preferably, all the coordinating hetero atoms are 'nitrogen atoms. The ligand L of formula (B) preferably comprises at least two substituted or unsubstituted heteroaryl groups in the four side groups. The heteroaryl group is preferably a pyridin-2-yl group and, if substituted, preferably a methyl- or ethyl-substitutec^pyridin-2-yl group. More preferably, the heteroaryl group is an unsubstituted pyridin-2-yl group. Preferably, the heteroaryl group is linked to methylamine, and preferably to the N atom thereof, via a methylene group. Preferably, the ligand L of oformula (B) contains at least one optionally substituted amino-alkyl side group, more preferably two amino-ethyl side groups, in particular 2-(N-alkyl)amino-etiiyl or 2-(N,N-diaIkyl)amino-ediyl. •■J Thus, in formula (B) preferably R1 represents pyridin-2-yl or R2 represents pyridin-2-yl-methyl. Preferably R2 or R1 represents 2-amino-ethyl, 2-(N-(m)ethyl)amino-ethyl or 2-(N,N-di(m)ethyl)amino-ethyl. If substituted, R5 preferably represents 3-methyl pyridin-2-yl. R3 preferably represents hydrogen, benzyl or methyl. Examples of preferred ligands L of formula (B) in their simplest forms are: (i) pyridin-2-yl containing ligands such as: N,N-bis(pyridto-2-yl-methyl)-bis(pyridin-2-yl)methylamine; NJ4-bis(pyrazol-1 -yl-methyl)-bis(pyridin-2-yl)methylamine; N^-bis(imidazol-2-yl-methyl)-bis(pyridin-2-yl)rnethylarnine; N,N-bis(l ,2,4-triazol-1 -yl-methyl)-bis(pyridin-2-yl)methylamine; N,N-bis(pyridm-2-yl-methyl)-bis(pyrazol-1 -y l)me thy lamine; N^-bisCpyridin^-yl-methyl^bisCirriidazol^-yOrnethylariiine; N,N-bis(pyridin-2-yl-methyl)-bis( 3,2,4-triazol-1 -yl)methylamine; N,N-bis(pyridin-2-yl-methyl)-1,1 -bis(pyridin-2-yl)-1 -aminoethane; N,N-bis(pyridin-2-yl-methyl)-1,1 -bis(pyridin-2-yl)-2-phenyl-1 -aminoethane; N.N-bis(pyrazol-1 -yl-methyl)-1,1 -bis(pyridin-2-y 1)-1 -aminoediane; N,N-bis(pyrazol-l -yl-methyl)-1,1 -bi$(pyridin-2-yl)-2-phenyl-1 -aminoethane; N,N-bis(imidazol-2-y!-methyl)-1,1 -bis(pyridin-2-yl> 1 -aminoethane; N,N-bis(imidazol-2-yl-methyl>-1,1 -bis(pyridin*2-yl)-2-phenyl-1 -aminoethane; N,N-bis(l ,2,4-triazol- r-yl-methyl)-1,1 -bis(pyridin-2-yl)-1 -aminoethane; N,N-bis(i ,2,4-triazol-1 -yljmethyl)-1,1 -bis(pyridin-2-yl)-2-phenyl-1 -aminoethane; N,N-bis(pyridin-2-yl-methyl)-1,1 -bis(pyrazol-1 -yl)- J -aminoethane; N,N-bis(pyridin-2-yl-methyl)-1,1 -bis(pyrazol-1 -yl>2-pheny I-1 -aminoethane; N,N-bis(pyridin-2-yl-methyl)-1,1 -bis(imidazol-2-yl> 1 -aminoethane; N,N-bis(pyridin-2-yl-methyl)-1,1 -bis(imidazol-2-yl)-2-phenyl-1 -aminoethane; N,N-bis(pyridin-2-yl-methyl>l ,1 -bis(l ,2,4-triazol-f-yl)-1 -aminoethane; N,N-bis(pyridin-2-yl-methyl)-1,1 -bis( 1,2,4-triazol-1 -yl> 1 -aminoethane; N,N-bis(pyridin-2-yl-methyl)-l, 1 -bis(pyridin-2-yl)-1 -aminoethane; N,N-bis(pyridin-2-yl-methyl)-l, 1 -bis(pyridin-2-yl>-1 -aminohexane; N,N-bis(pyridin-2-yl-methyl)-1,1 -bis(pyridin-2-yl)-2-phenyI-1 -aminoethane; N,N-bis(pyridin-2-yl-methyl)-l, 1 -bis(pyridin-2-yl)-2-(4-sulphonic acid-phenyl> 1 -aminoethane; N,N-bis(pyridtn-2-yl-methyl}-1,1 -bis(pyridin-2-yl)-2-(pyridin-2-yl)-1 -aminoethane; N^-bis(pyridin-2-yl-methyl)-l, 1-bis(pyridin-2-yi)-2-(pyridin-3-yl>-i-aminoethane; N,N-bis(pyridin-2-yl-methyl)-1,1 -bis(pyridin-2-yI)-2-(pyridin-4-yl>-1 -aminoethane; N,N-bis(pyridin-2-yl-methyl)-1,1 -bis(pyridin-2-yl)-2-( 1 -alkyl-pyridinium-4-yl)-1 -aminoethane; _ N,N-bis(pyridin-2-yl-methyl)-1,1 -bis(pyridin-2-yl)-2-( 1 -alkyl-pyridinium-3-yl)-1 -aminoethane; N,N-bis(pyridin-2-yl-methyl)-1,1 -bis(pyridin-2-yl)-2-(1 -aikyl-pyridinium-2-yl)-1 -aminoethane; (ii) 2-amino-ethyl containing ligands such as: N,N-bis(2-(N-alkyl)amino-ethyl)-bis(pyridin-2-yl)methylamine; N^-bis(2-(N-alkyI)amino-ethyl)-bis(pyrazo]-1 -yl)methylamine; N,N-bis(2-{N-alkyl)amino-ethy])-bis(iinida2ol-2-yl)methylamine; N,N-bis(2-(N-alkyl)amino-ethyl)-bis( 1,2,4-triazol-1 -yl)methylamine; N,N-bis(2'(N,N-dialkyl)amino-etiiyl>bis(pyridin-2-yl)methylamine; N,N-bis(2-(N,N-dialkyl)amino-ethyl)-bis(pyra2oI-1 -yi)methylamine; N^I-bis(2-(N,N-dialkyl)amino-ethyl)-bis(imida2ol-2-yI)methylam'ine; N^-bis(2-(N,N-dialkylo)amino-ethyl)-bis( 1,2,4-triazol-1 -yl)methylamine; N,N-bis(pVridin-2-yl-methyl)-bis(2-aminO'ediyl)methylamine; N^J-bis(pyrazol-l-yl-methyl)-bis(2-amino-ethyl)methylajmine; N^N-bis(imida2ol-2-yl-methyI)-bis(2-4unino-etliyi)methyiamine; N,N-bis( 1 ^,4-triazol-1-yl-methyl)-bis(2-amino-ethyI)methylamine. More preferred ligands are: N^I-bis(pyridin-2-yl-methyl)-bis(pyridin-2-yl)inethy]amine, hereafter referred to as N4Py. N^-bis(pyridin-2-yl-melhyl)-l,l-bi;;(pyridin-2-yl)-l-amboethaiie, hereafter referred to as MeN4Py, N,N-bis(pyridin-2-yl-methyl)-1,1 -bis(pyridin-2-yl)-2-phenyl-1 -aminoethane, hereafter referred Jo as BzN4Py. In an alternative fourth embodiment, the organic substance forms a complex of the general formula (A) including a ligand (B) as defined above, but with the proviso that R3 does not represent hydrogen. In a fifth embodiment of the second variant, the organic substance forms a complex of the general formula (A) as defined above, but wherein L represents a pentadentate or hexadentate iigand of general formula (C): R'R'N-W-NR'R2 wherein each R1 independently represents -R3-V, in which R3 represents optionally substituted alkylene, alkenylene, oxyalkylene, aminoalkylene or alkylene ether, and V represents an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl; W represents an optionally substituted alkylene bridging group selected from -CH2CH2-VCH2CH2CH2-, -CH2CH2CH2CH2-, -CH2-C6H4-CH2-, -CH2-C6H1(rCH2-, and -CH2-CioH6-CH2s and _ V R represents a group selected from R1, and alkyl, aryl and arylalkyl groups optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulphonate, amine, alkylamine and wherein R4 is selected from hydrogen, alkanyl, alkenyl, arylalkanyl, arylalkenyl, oxyalkanyl, oxyalkenyl, aminoalkanyl, arninoalkenyl, alkanyl ether and alkenyl ether. The ligand L having the general formula (C), ::s defined above, is a penLidentate ligand or, if R1=R2, can be a hexadentate ligand. As mentioned above, by 'pentadentate' is meant that five hetero atoms can coordinate to the metal M ion in the metal-complex. Similarly, by 'hexadentate' is meant that six heiero atoms can in principle coordinate to the metal M ion. However, in this care it is believed that one of the arms will not be bound in the complex, so that the hexadentate ligand will be penta coordinating. In the formula (C), two hetero atoms are linked by the bridging group W and one coordinating hetero atom is contained in each of the three R.' groups. Preferably, the coordinating hetero atoms are nitrogen atoms. The ligand L of formula (C) comprises at least one optionally substituted heteroaryl group in each of the three R1 groups. Preferably, the heteroaryl group is a pyridin-2-yI group, in particular a methyl- or ethyl-.substitwed pyridin-2-yl group. The heteroaryl group is linked to an N atom in formula (C), preferably via an alkylene group, more preferably a methylene group. Most preferably, the heteroaryl group is a 3-methyl-pyridin-2-yl group linked to an N atom via methylene. The group R2 in formula (C) is a substituted or unsubstituted alkyl, aryl or arylalkyl group, or a group R1. However, preferably R2 is different from each of the groups R1 in the formula above. Preferably, R2 is methyl, ethyl, benzyl, 2-hydroxyethyl or 2-methoxyethyl. More preferably, R2 is methyl or ethyl. V The bridging group W may be a substitated or unsubstituted alkylene group selected from -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CHJ-C^-CHJ-, -CH2-C6H,0-CH2-, and -CH2-C,oH6-CH2- (wherein -C&Rr, -C^o-, -CJOH6- can be oriho-,para~, or meta-C&h,-, -C6H10-, -C10H6-). Preferably, the bridging group W is an ethylene or 1»4-butylene group, more preferably an ethylene group. Preferably, V represents substituted pyridin-2-yl, especially methyl-substituted or ethyl-substituted pyridin-2-yJ, and most preferably V represents 3-methyl pyridin-2-yl. Examples of preferred ligands of formula (C) in their simplest forms are: N-meAyl-N,N'^'-tris(3-memyl-pyridm-2-ylmethyl)emylene-l,2-diarrune; N-ethyl-N^J'^'-tris(3-methyl-pyridin-2-ylmethyl)ethylene-1,2 -diamine; N-benzyl-N^l'.N'-trisfS-methyl-pyridin^-yii-nethyOethylene-l^-diamine; N-(2-hydroxyemyl)-N,N'J^,-tris(3-methyl-p>7idin-2-ylmethyl)eUiylene-lJ2-N,N\N,-tris(3-methyl-pyridin-2-ylmethyl)ethylene-l,2-diamine; N-methyl-N^',N'-tris(5-methyl-pyridin-2-yli:iethyl)ethylene-l,2-diamine; N-ethyl-N^,^I,-tris(5-methyl-pyridin-2-ylmeihyl)ethylene-1,2 -diamine; N-benzyl-N,N',N'-tris(5-methyl-pyridin-2-ylrnethyl)ethylene-l,2-diamine; N~(2-hydroxyethyl)-N,N,,N'-tris(5-methyl-pyndin-2-ylmethyl)ethylene-l^-diamme; N^-methoxyethyl^M.N'.N' -tris(5-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine; N-methyl-NJ^',N'-tris(3-ethyl-pyridin-2-ylmcthyl)ethylene-l,2'diamine; N-ethyl-N,N',N,-tri?(3-ethyl-p>Tidin-2-ylmethyl)ethylene-l,2-diamine; N-ben^l-N>3'^^tris(3-ethyl-pyridin-2-ylir>ethyl)ethylene-l,2-diamine; NK2-hydroxyerhyl)-N^\N,-tris(3-ethyl-pyridin-2-ylmetIiyI)ethylene-1.2-diamine; N-(2-methoxyethyl)-N,N',N,-tri£(3-e*hyl-pyridin-2-ylrnethyl)ethylene-l,2-diam;ne; N-methyVN)N',N'-tris(5-ethyl-pyridin-2-y]methyl)ethylene-l,2-diamine, N-ethyl-N,N',N'-tris(5-ethyl-pyridin-2-ylmethyl)ethylene-1,2-diamine; N-benzyl-N,N'>N'-tris(5-ethyl-pyridin-2-ylmetfiyl)etlrylene-M-diamine; and ° N-{2-memoxyethyl)-N,N,^,-tris(5-ethyl-pyridin-2-ylmethyl)ethylene-l,2-diamine. More preferred ligands are: N-methyl-N^'^'-tris(3-methyl-pyridin-2-ylmethyl)ethylene-l ^-diamine; N^thyl-N,N'^'-tris(3-methyl-pyridin-2-ylrnethyl>ethyIene-l,2-diamir.e; N-benzyl-N,N\N'-tris(3-methyl-pyndin-2-ylnr^thyl)ethylene-l,2-diamine; N-(2-hydroxyethyl)-N^",N'-iris(3-methyl-pyridin-2-ylinethyl)ethylene-l>2-diamine; and N^2-methoxyethyl)-N,N,^,-tris(3-niethyl-pyridin-2-ylmethyl)ethylene-1,2-d iamine. The most preferred ligands are: N-methyl-N^N',N'-tris(3-methyl-pyridin-2-ylraethyl)cthylene-1,2-diamine; and N-ethyl-N^'^'-trisCS-methyl-pyridin^-ylmethyr^thyJene-l^-diainine. Preferably, the metal M in formula (A) is Fe or Mn, more preferably Fe. Preferred coordinating species X in formula (A) may be selected from R°OH, NR63, R6CN, R600\ R6S\ R60\ R6COO\ OCN\ SCN\ N3', CN\ F, C\\ Br", V, 02\ N03", 2 2 3 » » NO2", SO4 , SO3 , PO4 and aromatic N donors selected from pyridines, pyrazmes, pyrazoles, pyrroles, imidazoles, benzimidazoles, pyrimidines, triazoles and uiiazoles, with R6 being selected from hydrogen, optionally substituted alkyi and optionally substituted aryl. X may also be the species LMO' or LMOO", wherein M is a transition metal and L is a ligand as defined above. The coordinating species X is preferably selected from CH3CN, H20, F, Cl\ Br*, OOH', R6COO", R60\ LMO-, and LMOO' wherein R6 represents hydrogen or optionally substituted phenyl, naphthyl, or C1-C4 alkyl. " The courAer ions Y in formula (A) balance the charge z on the complex formed by the ligand L, metal M and coordinating species X. Thus, if the charge z is positive, Y may be an anion such as R7COO\ BPb/, CIO4", BF/, PF6", R7S03\ R7SO„", S042\ N03", F, CI", Br\ or I", with R7 being hydrogen, optionally substituted alkyl or optionally " substituted aryl. If z is negative, Y may be a common cation such as an alkali metal, alkaline earth metal or (alkyl)ammonium cation. Suitable counter ions Y include those which give rise to the formation of storage-stable solids. Preferred counter ions for the preferred metal complexes arc selected from R7COO\ C1CV, BF4\ PF6\ R7SOj' (in particular CF3SO3'), R7S04\ S042", N03\ F, CI", Br", and I", wherein R7 represents hydrogen or optionally substituted phenyl, naphthyl or C1-C4 alkyl. It will be appreciated that the complex (A) can be formed by any appropriate means, including in situ formation whereby precursors of the complex are transformed into the active complex of general formula (A) under conditions of storage or use. Preferably, the complex is formed as a well-defined complex or in a solvent mixture comprising a salt of the metal M and the ligand L or ligand L-generating species. Alternatively, the catalyst may be formed in situ from suitable precursors for the complex, for example in a solution or dispersion containing the precursor materials. In one such example, the active catalyst may be formed in situ in a mixture comprising a salt of the metal M and the ligand L, or a ligand L-generating species, in a suitable solvent. Thus, for example, if M is iron, an iron salt such as FeS04 can be mixed in solution with the ligand L, or a ligand L-generating species, to form the active complex. In another such example, the ligand L, or a ligand L-generating species, can be mixed with metal M ions present in the substrate or wash liquor tc form the active catalyst in situ. Suitable ligand L-generating species include metal-free compounds or metal coordination complexes that comprise the ligand L and can be"substituted by metal M ions to form the active complex according the formula (A). ThereforeVin alternative fourth and fifth embodiments, the organic substance is a compound of the general formula (D): [{M'aL}bXc]2Yq in which M' represents hydrogen or a metal selected from Ti, V, Co, Zn, Mg, Ca, Sr, Ba, Na, K, and Li; X represents a coordinating species; a represents an integer in the range from 1 to 5; b represents an integer in the range from 1 to 4; c represents zero or an integer in the range from 0 to 5; z represents the charge of the compound and is an integer which can be: positive, zero or negative; Y represents a counter ion, the type of winch is dependent on the charge of the compound; q = z/[charge Y); and L represents a pentadentate ligand of general formula (B) or (C)oas defined above. In a fourth embodiment of the first variant, the organic substance comprises a macrocyclic ligand of formula (E): V Z'Q.2 A'-Y' Y'-A2J wherein Z and Z are independently selected from monocyclic or polycyclic aromatic ring structures optionally containing one or more heteroatoms, each aromatic ring structure bejng substituted by one or more substituents; Y1 and Y2 are independently selected from C, N> 0, Si, P and S atoms; A1.and A2 are independently selected from hydrogen, alkyl, alkenyl and cycloalkyl (each of alkyl, alkenyl and cycloalkyl) being optionally substituted by one or more groups selected from hydroxy, aryl, heteroaryl, sulphonate, phosphate, electron donating groups and elec*-on withdrawing groups^ and groups of formulae (G')(G2)N-, G3OC(0)-, G30- and G3C(0>-, wherein each of G1, G2 and G3 is independently selected from hydrogen and alkyl, and electron donating and/or withdrawing groups (In addition to any amongst the foregoing); i and j are selected from 0, 1 and 2 10 complete the valency of the groups Y and Y2; each of Q'-Q4 is independently selected from groups of formula wherein 10>a+b+o2 and d>= 1; each Y3 is independently selected from -0-,-S-, -SO-, -SO}-, -(G')N- (wherein G1 is hereinbefore defined), -C(0>, arylene, heteroarylene, -P- and -P(0>; each of A3-A6 is independently selected from the groups hereinbefore defined for A1 and A2; and wherein any two or more of A'-A6 together form a bridging group, provided that if A1 and A2 are linked without simultaneous linking also to any of A3-A°, then the bridging group linking A1 and A2 must comain at least one carboayl group. In the ligands of formula (E), unless specifically stated to the contrary, al! alkyl, hydroxyalkyl alkoxy, and alkenyl groups preferably have from 1 to 6, more preferably from 1 tcyt carbon atoms. Moreover, preferred electron donating groups include alkyl (e.g. methyl), alkoxy (e.g. methoxy), phenoxy, and unsubstituted, monosubstituted and disubstituted amine groups. Preferred electron withdrawing groups include nitro, carboxy, sulphonyl and halo groups. The ligands of formula (E) may be used in the form of complexes with an appropriate metal or, in some cases, in non-complexed foi m. hi the non-coup!exed form, they rely upon complexing with a metal supplied in the form of a separate ingredient in the composition, specifically provided for supplying that metal, or upon complexing with a metal found as a trace element in tap water. However, where the ligand alone or in complex form carries a (positive) charge, a counter anion is necessary. The ligand or complex may be formed as a neutral species but it is often advantageous, for reasons of stability or ease of synthesis, to have a charged species with appropriate anion. Therefore, in an alternative fourth embodiment, the ligand of formula (E) is ion-paired with a counter ion, which ion-pairing is denoted by formula (F): [HxL]lYq wherein H is an hydrogen atom; Y is a counter anion, the type of which is dependent on the charge of the complex; x is an integer such that one or more nitrogen aioms in L is protonated; z represents the charge of the comp:ex and is an integer which can be positive or zero; q=z/[charge of Y]; and L is a ligand of formula (E) as defined above. \ In a further alternative fourth embodiment, '.he organic substance forms a metal complex of formula (G) based on the ion pairing of formula (F) thus: [MxL]zYq wherein L, Y, x, z and q are as defined for formula (F) above and M is a metal selected from manganese in oxidation states II-V, iron II-V, copper I-I1J, cobalt I-UI, nickel I-EQ, chromium II-VI, tungsten IV-VI, palladium V, ruthenium II-IV, vanadium III-IV and molybdenum IV-VI. Especially preferred are the complexes of formula (G) wherein M represents manganese, cobalt, iron or copper. In a preferred fourth embodiment, the organic substance forms a complex of the formula (H): z wherein M represents an iron atom in oxidation state II or III, a manganese atom in oxidation state II, III, IV or V, a copper atom in oxidation state I, II or III or a cobalt atom in oxiqation state II, III or IV, X is a group which is either a bridge or is not a bridge between iron atoms, Y is a counter ion, x and y being >=1, 0= For the avoidance of doubt, "==" means "greater than or equal to". Preferably, in the complex of formula (H), M :epresents an iron atom in oxidation state II or III or a manganese atom in oxidation state H, IE, IV, or V. Preferably the oxidation state of M is III. When M is iron, preferably the complex of formula (K) is in the form of a salt of iron (inoxidised state) dihalo-2,1 l-4iazo[3.3](2,6)pyridinophane, dihalo-4~methoxy-2,l 1-diazo[3.3] (2,6) pyridinophane and mixtures thereof, especially in the form of the chloride salt. When M is manganese, preferably trie complex of formula (H) is in the form of a salt of manganese (in oxidised state) N, N'-dimethyl-2,l l-diazo[3.3](2,6)pyridfnophane, especially in the form of the monohexafluo.-ophosphate salt. Preferably, X is selected from H20, OH*, G2\ SH\ S2", S042", NR9R10\ RCOO", NR9R10RU, CI", Br", F, N3" and combinations thereof wherein R9, Rio and R| 1 are independently selected from -H, CM alkyl and aryl optionally substituted by one or more electron withdrawing and/or donating groups. More preferably, X is a halogen, u especially a fluoride ion. In the formulae (F), (G) and (H), the anionic counter ion equivalent Y is preferably selected from CI", Br", I', N03\ C104\ SOT, PF6-, RS03\ RS04", CF3SO3", BPh4*, and OAc". A cationic counter ion equivalent is preferably absent. In formula (H), R| and R2 are preferably both hydrogen. R3 and R4 are preferably CM alkyl, especially methyl. R$-R« are each preferably hydrogen. According to the values of x and y, the aforementioned preferred iron or manganese catalysts of formula (H) may be in the forn; of a monomer, dimer or oligomer. Without . being bound by any theory, it has been conjectured that in the raw material or detergent composition state, the catalyst exists mainly or solely in monomer form but could be converted to dimer, or even oligomeric fori a, hi the wash solution. In typical washing compositions the level of the organic substance is such that the in-use level is from luM to 50mM, with preferred in-use levels for domestic laundry operations falling in the range 10 to 100 }iM, Higher levels may be desired and applied in industrial textile bleaching processes. Preferably, the aqueous medium has a pH in the range from pH 6 to 13, more preferably from pH 6 to 11, still more preferably from pH 8 to 11, and most preferably from pH 8 to 10, in particular from pH 9 to 10. The method of the present invention has particular application in detergent bleaching, especially for laundry cleaning. Accordingly, in another preferred embodiment, the method uses the organic substance in a liquor that additionally contains a surface-active ° material, optionally together with detergency builder. The bleach liquor may for example contain a surface-active material in an amount of from 10 to 50% by weight. The surface-active material may be naturally derived, such as soap, or a synthetic material selectedjrom anionic, nonionic, amphoteric, zwitterioivc, cationic actives and mixtures thereof. Many suitable actives are commercially available and are fully described in the literature, for example in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch. Typical synthetic anionic surface-actives are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl groups containing from about 8 to about 22 carbon atoms, the term "alkyl" being used to include the alkyl portion of higher aryl groups. Examples of suitable synthetic anionic detergent compounds aie sodium and ammonium alkyl sulphates, especiaJiy those obiai.ied by sulphating higher (Cs-Cig) alcohols produced, for example, from tallow or coconut oil; sodium and ammonium alkyl (C9-C20) benzene sulphonates, particuarl;- scdium linear secondary alkyl (C10-C15) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil fatty acid monoglyceride sulphates and sulphonates; sodium and amnionium salts of sulphuric acid esters of higher (Cg-Cn) fatty alcohol alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and ammonium salts of fatty acid amides of methyl taurine; alkane r.ionosulphonates such as those derived by reacting alpha-olefins (Cg-C2o) with sodium bisulphite and those derived by reacting paraffins with SO2 and CI2 and then hydroly:»ing with a base to produce a random sulphonate; sodium and ammonium (C7-C12; diulkyl sulphosuccinates; and olefin sulphonates, which term is used to describe Material made by reacting olefins, particularly (C10-C20) alpha-olefins, with SO, and then neutralising ind hydrolysing the reaction product. The preferred anionic detergent compounds are sodium (CIO-CIS) alkylbenzene sulphonates, and sodium (Ci6-Cig) alkyl ether sulphates. Examples of suitable nonionic surface-active compounds which may be used, preferably together with the anionic surface-active compounds, include, in particular, the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C6-C22) phenols, generally 5-25 EO, i.e. 5-25 units of ethylene oxides per moiecule; and the condensation products o^aliphatic (Cg-Cis) primary or secondary linear or branched alcohols with -ethylene oxide, generally 2-30 EO. Other so-called nonionic surface-actives include alkyl polyglycosides, sugar esters, long-chain tertiary amine oxides, long-chain tertiary phosphine oxides and dialkyl sulphoxides. Amphoteric or zwitterionic surface-active compounds can also be used in the compositions of the invention but this is not normally desired owing to their relatively high cost. If any amphoteric or zwitterioni;; detergent compounds are used, it is generally in small amounts in composition: based on the much more commonly uied synthetic anionic and nonionic actives. The detergent bleach liquor will preferably comprise from 1 to 15 % wt of anionic surfactant and from 10 to 40 % by weight of nonionic surfactant.. In a further preferred embodiment, the detergent active system is free from Ci^Cn fatry acid soaps. The bleach liquor may also contains a detei gency builder, for example in an amount of from about 5 to 80 % by weight, preferably from about 10 to 60 % by weight. Builder materials may be selected from 1) calcium sequestrum" materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof. Examples of calcium sequestrum builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate; nitrilotriacetic acid and its water-soluble salts; the alkali metal salts of carboxymethyloxy succinic acid, ethylene diamine tetraacetic acid, oxydisuccinic acid, mellitic acid, benzene polyearboxylic acids, citric acid; and polyacetal carboxylates as disclosed in US-.V4, i44,226 and US-A-4,146,495. Examples of precipitating builder materials include sodium orthophesphate and sodium carbonate. • Example^of calcium ion-exchange builder materials include the various rypes of water-insoluble crystalline or amorphous ahunino silicates, oC which zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070. In particular, the bleach liquor may contajn any one of the organic and inorganic builder materials, though, for environmental reasons, phosphate builders are preferably omitted or oruy useu in very small amounts. Typical builders usable in the present invention are, for example, sodium carbonate, calcite/carl.omite, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxyrnethyloxy malonat--, carboxymethyloxy succinaxe and water-insoluble crystalline or amorphous alumincsilicatc builder materials, each of which can be used as the main builder, either alone or in admixture with minor amounts of other builders or polymers as co-builder. It is preferred that the composition contains not more than 5% by weight of a carbonate builder, expressed as sodium carbonate, mere preferably not more than 2.5 % by weight to substantially nil, if the composition pH lies in the lower alkaline region of up to 10. Apart from the components already mentioned, the bleach liquor can contain any of the conventional additives in amounts of which such materials are normally employed in fabric washing detergent compositions. Examples of these additives include buffers such as carbonates, lather boosters, such as alkanoiamides, particularly die monoethanol amides derived from palmkemel fatty acids and coconut fatty acids; lather depressants, such as alkyl phosphates and silicones; anti-redeposition agents, such as sodium carboxymethyl cellulose and alkyl or substituted aikyl cellulose ethers; stabilisers, such as phosphonic acid derivatives (i.e. Deques;® types); fabric softening agents; inorganic salts and alkaline buffering agentg, such as sodium sulphate and sodium silicate; and, usually in very small amounts, fluorescent a^enis; perfumes; enzymes, such as proteases, celluloses, lipases, amylases and oxidases; germicides and colourants. Transition metal sequestrants such as EDTA, and phosphonic acid derivatives such as EDTMP (ethylene diamine tetra(rnethylene phosphonate)) may also be included, in addition to the organic substance specified, for example to improve the stability sensitive ingredients such as enzymes, fluorescent agents and perfumes, but provided the composition remains bleach'.ng effective. However, the treatment composition containing the organic substance, is preferably substantially, and more preferably completely, devoid of transition metal'sequestrants (other than the organic substance). Whilst the present invention is based on the catalytic bleaching of a substrate by atmospheric oxygen or air, it will be appreciates} that small amounts of hydrogen peroxide or peroxy-based or -generating systems inay be included in the treatment composition, if desired. Preferably, however, the composition will be devoid of peroxygen bleach or peroxy-based or -generating bleach systems. The invention will now be further illustrateu by way of the following ncn-limiting examples: EXAMPLES Example 1 This example describes a synthesis of a cata;yst according to formula (A): (i) Preparation of MeN4Py ligand: The precursor N4Py.HC104 was prepared as follows: To pyridyl ketone oxim (3 g, 15.1 mmol) wns added ethanol (15 ml), concentrated ammonia solution (15 mL) and NHjOAc (1.21 g, 15.3 mmol). The solution was warmed until reflux. To this solution was added 4.64 g Zn in small portions. After the addition of all Zn, the mixture was refluxed for 1 hour and allowed to cool to ambient temperature. The solution was filtered and water (15 ml) was added. Solid NaOH was added until pH»10 and the solution was extracted with CH2CI2 (3 x 20 ml). The organic layers were dried over Na2$0^ and evaporated until dryness. 3is(pyridir,-2-yl)methylamine (2.39 g, 12.9 mmol) was obtained as a colourless oil in 86% yield, showing the following analytical characteristics: .,HNMR(360 MHz, CDC13): 5 2.64 (s, 2H, m2), 5.18 (s, IH, CH), 6.93 (m, 2H, pyridine), 122 (m, 2H, pyridine), 7.41 (m, 211, pyridine), 8.32 (m, 2H, pyridine); 13C NMR(CDC13):6 62.19(CH), 121.73 (CH), 122.01 (CH), 136.56 (CH), 149.03 (CH), 162.64 (Cq). To picolylc^loride hydrochloride (4.06 g, 24.3 mrnol) was added, at 0°C, 4.9 ml of a 5N NaOH solution. This emulsion was added by means of a syringe to bis(pyridin-2-yl)methylamine (2.3 g, 12.4 mmol) at 0°C. Another 5 ml of a 5N NaOH solution was added to this mixture. After warming to ambient temperature, the mixture was stirred vigorously for 40 hrs. The mixture was put in an ice bath and HCIO4 was added until pHcool to ambient temperature, whereupon a light-brown solid precipitated which was collected by filtration and washed with cold water and air-dried (l."47 g). From 0.5 g of the perchlorate salt of N4Py prepared as described above, the free amine was obtained by precipitating the salt with 2N NaOH and subsequently by extraction with CH2CI2. To the free amine w^s added under argon 20 ml of dry tetrahydrofuran freshly distilled from LiAJH*. The mixture was stirred and cooled to -70 °C by an alcohol / dry ice bath. Now 1 ml of 2.5 N tutyllithium solution in hexane was added giving an immediate dark red colour. The mixture was allowed to warm to -20 CC and now 0.1 ml of methyl iodide was added. The temperature was kept to -10 C for 1 hour. Subsequently 0.5 g of ammonium chloride was added and the mixture was evaporated in vacuo. To the residue water was added and die aqueous layer was extracted with dichloromethane. The dichloromethane layc;r was dried on sodium sulphate, filtered and evaporated giving 0.4 g residue. The residue w;>s purified by crystallisation from ethyl acetate and hexane giving 0.2 g of creamish powder (50% yield) showing the following analytical characteristics: 'HNMR (400 MHz, CDCI3): 5 (ppm) 2.05 (s, :H, CH3), 4.01 (s, 4H. CH2), 6.92 (m, 2H, pyridine), 7.08 (m, 2H, pyridine), 7.39 (m, 4H pyridine), 7.60 (m 2H, pyridine), 7.98 (d, 2H, pyridine), 8.41 (m, 2H pyridine), 8.57 (m, 2H, pyridine). 13C NMR (100.55 MHz, CDCI3): 6 (ppm) 21.7 (CH3), 58.2 (CH2), 73.2 (Cq). 121.4 (CH), 121.7 (CH), 123.4 (CH), 123.6 (CH), 136.0 (CH), 148.2 (Cq), 148.6 (Cq), 160.1 (Cq), 163.8 (Cq). (ii) Synthesis of the complex [(MeN4Py)Fe(CH3CN)](C10 To a solution of 0.27 g of MeN4Py in 12 m! of a mixture of 6 ml acetonitrile and 6 ml methanol was added 350 mg Fe(C10 'H NMR (400 MHz, CD3CN): 5 (ppm) 2.15, (CKjCN), 2.28 (s, 3H. CH3), 4.2 (ab, 4H, CH2), 7.05 (d, 2H, pyridine), 7.38 (m, 4H, pyridine), 7.71 (2t, 4H pyridine), 7.98 (t, 2Hf pyridine), 8.96 (d, 2H pyridine), 9.06 (m, 2H, pyridine). UV/Vis (acetonitrile) [?anax, nm (e, M"! erf1)]: 331 (8400), 458 nn.j(6400). Anal.Calcd for C25H26Cl2FeN608: C, 46.11; H, 3.37; N, 12.41; CI, 10.47; Fe, .3.25. Found: C, 45.49; H, 3-95; N, 12.5; CI, 10.7; Fe, 8.12. Mass-ESP (cone voltage 17V in CH3CN): m/z 218.6 [MeN4PyFe]2r; 239.1 [MeN4PyFeCH3CN]2+. Example 2 This example describes a synthesis of a catalyst according to formula (A): (i) Synthesis of BzN4Py Hgand: To 1 g of theN4Py ligand prepared as described above, 20 ml of dry tetrahydrofuraii freshly distilled from LiAlFLj, was added under argon. The mixture was stirred and cooled to -70 °C by an alcohol / dry ice bath. Now 2 ml of 2.5 N butyllithium solution in hexane was added giving an immediate dark red colour. The mix was allowed to warm to -20°C and now 0.4 ml of benzyl bromididti was added. The mixture was allowed to warm up to 25 °C and stirring was continued over night. Subsequently 0.5 g of ammonium chloride was added and the mixture was evaporated in vacuo. To the residue water was added and the aqueous layer was extracted with dichloromethane. The dichloromethane layer was dried on sodium sulphate, filtered and evaporated giving 1 g brown oily residue. According to NMR spectroscopy, the product wa? not pure but contained no starting material (N4Py). The residue was used without further purification. (ii) Synthesis of the complex [(BzN4Py)Fe(CH3CN)l(C104)2. Fe(BzN4Py): To a solution of 0.2 g of the residue ob*.ai,ed by the previous described procedure in 10 ml of a mixture of 5 ml acetonitrile and 5 ml methanol was added 100 mg Fe(C104)2.6H20 immediately a da?k red colour formed. To the mix was added now 0.25 g of sodium perchlorate and ethylacetate \vas allowed to diffuse into the mixture overnight. Some red crystals were formed which were isolated by nitration and washed with methanol. In this way 70 mg of a rsd powder was obtained showing the following analytical characteristics: 1H NMR (400 MHz, CDjCN): 5 (ppm) 2.12, (s, 3H, CHjCN), 3.65 + 4.1 (ab, 4H, CH2), 4.42 (s, 2H, CH2-benzyl), 6.84 (d, 2H, pyridine), 7.33 (m, 4H, pyridine), 7.45 (m, 3 H, benzene) 7.65 (m, 4R benzene + pryidine); 8.08(m, 4H, pyridine), 8.95 (m, 4H pyridine). UV/Vis (acetonitrile) [Xmax, nm (e, M'! an1)): 380 (7400), 458 mn (5500). Mass-ESP (cone voltage 17V in CH3CN): rn/z 256.4 [BzN4Py]2+; 612 [BzN4PyFeC104)+ Example 3: ^ This example describes syntheses of catalysts according to formula (C)j All reactions were performed under a nitrogen atmosphere, unless indicated otherwise. All reagents and solvents were obtained from Aldrich or Across and used as received, unlessstated otherwise. Petroleum ether 4u-60 was distilled usii.g a rotavapor before using it as eluent. Flash column chromatography was performed using Merck silica gel 60 or aluminium oxide 90 (activity Il-III according to Brockmann). *H NMR (300 MHz) and PC NMR (75 MHz) were recorded in CDCh, unless stated otherwise. Multiplicities were addressed with the normal abbreviations using p for quintet. Synthesis of starting materials for ligand synthesis: Synthesis ofTV-benzyl amino acetonitrile, /V-benzyl amine (5.35 g, 50 mmol) was dissolved in a water: methanol mixture (50 mL, 1:4). Hydrochloric acid (aq., 30 %) was added until the pH reached 7.0. Adciec was NaCN (2.45 g. 50 inmol). After cooling to 0 °C, formaline (aq. 35 %, 4.00 £ 50 mmol) was added. The reaction was followed by TLC (aluminium oxide; EtOAt : E13N = 9:1) until benzylumine could be detected. Subsequently the methanol was e /aporated in vacuo and the remaining oil "dissolved" in water. The aqueous phase w 3 extracted with methylene chloride (3 x 50 mL). The organic layers were collected anc the solvent removed in vacuo. The residue was purified by Kugelrolvr distillation (p= /0 mm Hg, T ~ 120 °C) giving //-benzyl amino acetonitrile (4.39 g, 30 mmol, 60 %) as a colourless oil. 'HNMR: 8 7.37 - 7.30 (m, 5H), 3.94 (s, 2.H), 3.57 (s, 2H), 1.67 (br s, 1H); ,3C NMR: 6 137.74, 128.58, 128.46, 123.37, 127.93, 127.62, 117.60, 52.24, 36.19. Synthesis of//-ethyl amino acetonitrile. This synthesis was performed analogously to the synthesis reported for //-benzyl amino acetonitrile. However, defection was done by dipping the TLC plate in a solution of KMn()4 and heating the plate until bright spots appeared. Starting from ethylamine (2.25 g, 50 mmol), pure //-ethyl amino acetonitrile (0.68 g, 8.1 mmol, 16 %) was obtained as a slightly yellow oil. lHNMR: 5' 3.60 (s,2H), 2.78 (q, J = 7.1,211), 1.22 (br s, 1H}, 1.14 (t, J = 7.2, 3H); ,3CNMR: 8 117.78,43.08,37.01, 14.53. Synthesis of//-ethyl ethylene-l,2-diami«e. The synthesis was performed according to Hageman; J.Org.Chem.; 14; 1949; 616, 634, starting from /V-ethyl amino acetonitrile. Synthesis of/V-benzyl ethylene-l,2-diannne. Sodium hydroxide (890 mg; 22.4 mmol) "was dissolved in ethanol (96 %, 20 mL), the Upon addition of base (aq. NaOH, 5N) the product oiled out and was exiracted with chloroform (3 x 20 mL). After evaporation of the solvent in vacuo the !H NMR showed the presence of benzylamine. Separation was enforced by column chromatography (silica gel; MeOH : EtOAc : Et3N = 1:8:1) yielding the benzyl amine, followed by the solvent mixture MeOH : EtOAc : EtjN = 5:4:1. Detection was done hy using aluminium oxide as a solid phase in TLC, yielding pure //-benzyl ethylene-1,2-diamine (2.04 g, 13.6 mmol, 59%). 'HNMR: 6 7.33 - 7.24 (m, 5H), 3.30 (s, 2H), 2.82 (1,7= 5.7,'2H), 2.69 (t, J= 5.7, 2H), 1.46(brs,3H); 13CNMR: 5 140.37, 128.22, 127.93, 126.73,53.73,51.88,41.66. Synthesis of 2-acetoxymethyl-5-methyl pyridine. 2,5-Lutidine (31.0 g, 290 mmol), acetic acid (180 mL) and hydrogen peroxide (30 mL, 30 %) were heated at 70-80 "G for 3hours. Hydrogen peroxide (24 mL, 30 %) was added and the subsequent mixture heated for 16 hours at 60-70 °C. Most of the mixture of (probably) hydrogen peroxide, water, acetic acid, and peracetic acid was removed in vacuo (rotavap, water bath 50 °C until p = 20 mbar). The resulting mixture containing the jV-oxide was added dropwise to acetic anhydride heated under reflux. This reaction was highly exothermic, and was controlled by the dropping speed. After heating under reflux for an hour, methanol was added dropwise. This reaction was highly exothermic. The resulting mixture was heated under reflux foi another 30 minutes. After evaporation of the methanol (rotavap, 50 °C until p = 20 mbar), the resulting mixture v/as purified by Kugelrohr distillation (p = 20 mm Hg, T - 150 °C). The clear oil that was obtained still contained acetic acid. This wasljemoved by extraction (CfyCb, NaHC03 (sat.)) yielding the pure acetate of 2-acetoxymethyl-5-methyl pyridine (34.35 g, 208 mmol, 72 %) as a slightly yeilow oil. 'HNMR: 6 8.43 (s, 1H), 7.52 (dd, J= 7.8, J= 1.7, 1H), 7.26 (d,.7=7.2, 1H), 5.18 (s,2H), 2.34 (s,3H£ 2.15 (s, 3H); ,3CNMR: 6 170.09, 152.32, 149.39, 136.74, 131.98, 121.14, 66.31, 20.39, 17.66. Synthesis of 2-acctoxyincthyl-5-cthyi pyridine. This synthesis was performed analogously to the synthesis reported for 2 -acetoxymethyl-5-methyl pyridine. Starting from 5-ethyl-2-methyl pyridine (35.10 g, 290 mmol), pure 2-acetoxymctIiyl-5-ethyl pyridine (46.19 g, 258 mmol, 89%) was obtained as a slightly yellow oil. 'HNMR: 58.47(S, lH), 7.55 (d,./= 7.3, 1H), 7.29 (d,J= 8.1, !H), 2.67 (q,J= 7.8,2H), 2.14 (s, 3H), 1.26 (t, J'=7.77, 3K); 13CNMR: 5 170.56, 152.80, 149,11, 138.47, 135.89, 121.67, 6c .72,25.65, 20.78, 15.13. Synthesis of 2-acetoxymethyl-3-rnethyi pyridine. This synthesi? was performed analogously to the synthesis reported for 2-aceioxymethylo-meth/l pyridine. The only difference was the revers?] of the Kugelrohr distillation and the extraction. According to H NMR a mixture of die acetate and the coi responding alcohol was obtained. Starting from 2,3-picoline (31.0 g, 290 mmol), pure 2-acetoxymethy!-3-methyl pyridine (46.19 g, 258 mmol, 89%, calculated for pure acetate) was obtained as a slightly yellow oil. 'HNMR: 5 8.45(d,J=3.9, 1H), 7.50 (d,./= 8.4, 1H), 7.17 (dd. J= 7.8, J = 4.8, 1H), 5.24 (s, 2H), 2.37 (s, 3H), 2.14 (s, 3H). Synthesis of 2-hydroxyniethyl~5-niethyl pyridine. 2-Acetoxymethyl-5-methyl pyridine (30 g, 182 mmol) was dissolved in hydrochloric acid (100 mL, 4 N). The mixture was heated under reflux, until TLC (silica gel; triethylamine:ethyi acetaterpetroleum ether 40-60 = 1:9:19) showed complete absence of the acetate c (normally 1 hour). The mixture was cooled, brought to pH > 11, extracted widi dichloromemane (3 x 50 mL) and die solvent removed in vacuo. Pure 2- hydroxymethyl-5-methyl pyridine (18.80 g, 152 mmol, 84 %) was obtained by Kugelrohr distillation^p = 20 mm Hg, T = 130 °C) as a slightly yellow oil. 'HNMR: 6 8.39 (s, 1H), 7.50 (dd,.7=7.8, J =1.8, 1H), 7.15 (d,J= 8.1, 1H),4.73 (S, 2H), 3.83 (br s, 1H), 2.34 (s, 3H); ,3CNMR: 5 156.67, 148.66, 137.32, 131.62, 120.24. 64.12, 17.98. Synthesis of 2-hydroiymcthyI-5-ethyl pyridine. This synthesis was performed analogously to the synthesis reported for 2-.iyc;xxymeihyl-5-methyl pyridine. Starting from 2-acetoxymethylo-ethyl pyridine (-10 g, 123 mmol), pure 2-hydroxymethyl-5-ethyl pyridine (26.02 g, 189 imnol, 85 %) was cl.um.cd is a slightly yellow oil. 'HNMR: 58.40 (d,7- 1.2, 1H),7.52 (del, J= S.C, J =2.0, If I), 7.18 (d, 7-8.1, 1H). 4.74 (s, 2H), 3.93 (br s, 1H), 2.66 (q, J = 7.6, 2H), 1.26 (t, J = 7.5, 3H); ,3CNMR: 5 156.67, 148.00, 137.87, 136.13, 120.27, 64.07, 25.67, 15.28. Synthesis of 2-hydroxymethyl-3-methyl pyridine. This synthesis was performed analogously to the synthesis rep-or.ed for 2-.iyci:Oxyiueihyl-5-methy; pyridine. Starting from 2-acetoxymeuiyl-3-methy; pyridine (25g 'recalculated for the mixture), 152 mmol), pure 2-hydroxymethyl-3-methyl pyridine (IS.51 g, 126 mmol, S3 %) was obtained as a slightly yellow oi!. 'HNMR: 6 8.40 (d,.7=4.5, 1H)), 7.4' (c, J= 7.2, 1H), 7.15 (dd, J= 7.5, J= 5.1, 1H), 4.85 (br s, 1H), 4.69 (s, 1H), 2.22 (s. ?H); I3CNMR: 5 156.06, 144.97, 137.38, 129.53, 12!.91, 61.38, 16.30. (T) Synthesis of ligands: Synthesis of A^-methyl-///v/,^V-tris(pyridin-2-yiiueJhyl)ethylene-l,2-diamine (LI). The ligand LI (companitive) was prepared according to Bemal, Iva,i; Jensen, Irge Margrethe; Jensen, Kenneth B.; McKenzie, Ckisdnv J.; Toftlund, iians; Tuchagues, Jean-Piei^e; J.Chem.Soc.Dalton Trans.; 22; 1995; 3667-3676. Synthesis of A'-methyl-ArA,//'-tns(3-inetiiylpyridin-2-ylmethyl)ethyiene-l,2-diamine (L2, MeTrilen). 2-HydroxymethyI-3-meUiyl pyridine (5.00 g, 40.7 mmol) was dissolved in dichloromeiharie (30 mL). Thiom i chloride (30 mL) was added dropwise under cooling (ice bath). The resulting mix'.ua- was .stirred for 1 hour and the solvents removed in vacuo (rotavap, unui p = 20 mm llg, T = 50 °C). To the resultant mixture was added dichloro.nethane (25 mL). Sub^qu::,i.i!y NaOH (5 K, v....) w&> added dropvvise until the pH (.qua) > 11. The .e;. ; ti.cn v/aj quite vigorous in the beginning, since part of the ihionyl chloride was stii, p.esen:. //-methyl ethylene-1,2-diamine (502 mg, 6.8 mmol) ana additional NaOlI '5 N, 10 mL) were sdde.i. The reaction mixture was stirred at room temperature JO: 45 nours. The mixture was poured into water (200 mL), and the pH checked (> 14, otherwise addition of rTiOH (aq. :>N)). The reaction mixture was extracted with dichiorornethane (3 or 4 x 50 mL, until no product could be detected by TLC). The combined organic phases were dried and the solvent removed in vacuo. Purification was enforced as described before, yielding A'-methyl-7/^V^V,-tris(3-methy!p>Tidin-2-ylmethyl)cth}'lei;e-l,2-diamine as a slightly yellow oil. Purification was enforced by column chromatography (aluminium c;-;ide 90 (activity II-III according to Broclunann); triet.hylam.ine : ethyl acetate : petroleum ether 40-60 = 1:9:10) until the impurities were removed according to TLC (aluminium oxide, same eluent, Rf « 0.9). The compound was elu;ec usin. e:hylacetate : trkihyl amine = 9:1. Mmethyl-Af^^-tri. 'HNMR: 5 8.36 (d, J = 3.0, 3H), 7.40 - 7.37 ,:n, 3H), 7.11-7.06 (m, 3H). 3.76 (s, AH), 3.48 (s, 2H), 2.76 - 2.71 (m, 2H), 2.53 - 2. ,3CNMR: 6 156.32, 156.77, 145.83, 145.67 1J7.61, 133.14, 132.72, 3 22.10, 121.88,62.32,59.73,55.19,51.87,42.37, 18.22., 17.80. Synthesis of;V-ethyl-ArA,^-tris(3-methyl|)yrii3rii-2-y!.methyI)ethykne-l,2-diaraine (L3, EtTrhNen). This synthesis is performed -inaiogously to the synthesis for L2. Starting from 2-hydroxymethylo -methyl pyridine (25.00 g, 203 mmol) and /V-eihyl ethylene-1,2-diamine (2.99 g, 34.0 mmol), A'-ethyi-.V,A\A'-tris(methy:p>Tidin-2--ylmethyl)ethylenc-l,2-diamine (L3, ! 1.49 H, 28.5 mmol, 84 %) was obtained. Column chromatography (aluminium oxide; Et3N : EtOAc : petroleum ether 40-60 = 1:9:30, followed by Et3N : EtOAc = 1:9). 'H NMR: 5 S.34 - 8.30 (m, SH), 7.40 - 7.3-, (in, 311). 7.09 - 7.03 (m, 3H). 3.71 (s, 4H), 3.58 (s, 2H), 2.64 - 2.59 (m, 2H), 2.52 • 2,17 (m, 2H), 2.43 - 2.36 (m, 2H), 2.31 (s, 3H), 2.10 (s, 6H), 0.87 (t, J - 7.2, 3H); 13CNMR: 5 157.35, 156.92, 145.65. 137.61, 133.14, 132.97, 122.09, 121.85,59.81, 59.28,51.98,50.75,48.02, 18.27, 17.30 11.36. Synthesis of Ar-benzyl-yV/vfl^-tns(3-c.ethylpyridiii-2-ylmethyl)ethylcne-lv2- diamine (L4, BzTrilen). Tins synthesis is performed analogously to the syndesis for L2. Starting from 2-hydroxymethyl-3-n,v,thyIpyridine (3.00 g 24.4 rnmol), and jV-benzyl ethylene- 1,2-diamine (610 mg, 4.07.irLn .1), ;V-b^iizyi-A;jV//-tris(3-m.iJiylpyridin-2- ylmethyi)ethylene-1,2-diamine (L4, 1.367 g. 2 93 mmol, 72 %) was obtained. Column chromatography (aluminium oxide; Et3N : Eiu/\c : petroleum ether 40-60 = i :9:10). 'H NMR: o 8.33 - 8.29 (m, 311), 7.3 • - 7.33 (m, 3H), 7.21 - 7.03 (m, 8H), 3.66 (s, 4H), 3.60 (s, 2H), 3.42 (s, 2H), 2.72 - 2.67 (n., 2H), 2.50 - 2.45 (m, 2H), 2.23 (s, 3H), 2.03 (s, 6H); ,3CNMR: 5 157.17, 156.96, 145.83, 145.75, 139.29, 137.91, 137.80, 133.45, 133.30,128.98, 127.85, 126.62, 122.28, : 22.22. 59.99, 58.83. 51.92, 51.54, 18.40, 17.95. Synthesis of jV-hydroxyethyl-Ayv,//!-t,is(3-]nethyipyridin-2-yimethyl)elhylene-l,2- diamine (L5). This synthesis is perfonned analogously to the synthesis for L6. Starting from 2-hydroxymethyl-3-methyl pyridine (3.49 g, 28.4 mmol), and A^-hydroxyethyl ethylene-1,2-diamine (656 mg 6.30 mmo1), after 7 days A^-hydroxyethyl-^Y'jV-tris(3- memylpyridin-2-ylmethyl)ethylei;e-l,2-d;;mii;iL' (L5, 379 mg, 0.97 mmol, 14 %) was obtained. 'HNMR: 8 8.3 i - 8.28 (m, 3H), 7.35 - 7.33 (m, 3H), 7.06 - 7.00 (.T., 3H), 4.71 (br s, 1H), 3.73 (s, 4H), 3.61 (s, 2H), 3.44 (:, ./= 5.1, 2H), 2.68 (s, 4H). 2.57 (t, J- 5.0,2H), 2.19 (s,3H), 2.10 (s,6H); 13CNMR: 5 157.01, 156.38, 145.9:, .45.80, 137.90, 137.83, 133.30, 131.89, 122.30, 121.97, 59.60, 59.39, 57.95, 56.67, 51.95, 51.22, 18.14, 17.95. Synthesis of 7V-:nethyJ-/i/A'»^',-^"is(5-niCihy:pyiiJai-2-ylmethy!)ethylene-;i,2-diamine(L6). 2-hydroxymethyl-5-methyl pyridiiie (2.70 g, 21.9 ni'nol) was dissolved in dichloromethane (25 inL). 'ITiionyl chloride (25 mL) was added cropwise under cooling (ice bath). The resulting mixture was t-i'n red for 1 hour and he solvents removed' in vacuo (rctavap, until p = 20 mm Hg, T + 35°C). The remaining oil was used directly in the synthesis of the ligands, since it was known from the literature that the free picolyl chlorides are somewhat unstable ai.d an highly lachrymatory. To the resultant mixture was added dichloromethane (25 mL) and //-methyl ethylene-1,2-diamine (360 mg, 4.86 mmol). Subsequently NaOH (5 N, aq.) was added dropwise. The reaction was quite vigorous in the beginning, since part of the ti.onyl chloride was still present. The aqueous layer was brought to pH - 10, and additional NaOH (5 N, 4.38 mL) was added. The reaction mixture was stir/ed until a samp If indicated complete conversion (7 days). The reaction mixture was extracted .-, ith dichloromethane (3 x 25 mL), The combined organic phases were dried and die solvent removed in vacuo. Purification was enforced by column chromatography (aluminium oxide 90 (activity II—III according to Brockmann); 'ieinylamine : eti. ,1 acetate : petroleum ether 40-60 = 1:9:10) until the impurities were removed according to TLC (aluminium oxide, same eluent, Rf-^ 0.9). The compound was eluted using ethyl acetate : diethyl amine = 9:1, yielding A-methyl-A'A'1 ^Mris(5-methy]pyridir,-2-ylmethyl)ethylene-l,2-diamine (L6, 685 mg, 1.76 mmel, 36 %) as a slightly yellow oil. 'HNMR: 5 8.31 (s, 3H) 7.43-7.35 (in, 5H), 7.21 (d, .7=7.8, 1H;, 3.76 [s, 4H), 3.56 (s, 2H), 2.74 - 2.69 (m, 2H), 2.63 - 2.58 (m, 211), 2.27 (s, 6H). 2 ; 6 (s, 3H); I3CNMR:V 8 156.83, 156.43, 149.23, 149.18, 136.85, 136.81, 131.02, 122.41, 122.30, 63.S3, 60.38, 55.53, 52.00, 42.76, 18.03. Synthesis of Ar-methyl-Arw'V,/v',-tris(5-ethylpyridJn-2-ylmethyl)ethylene-l,2-dianiine (L7). This synthesis is performed analogously to the synthesis for LC Starting from 2-hydroxymethyl-5-ethyl pyridine (3.00 g, 21.9 mmol), and A'-methyl ethylene-1,2- diamine (360 mg, 4.86 rnmol), after 7 da>s .V-inc:nyM/^TAMris(:>-eihylpyridin-2-ylmethyl)ethyler:e-i,2-diaminc (L7, 545 in;,, 1.26 ai.ol, 26 %) wa-; obtained. lHNMR: 6 8.34 (s, 3H), ..44 - 7.39 (::>., ;■:-:;, 7.26 (d, J- 6.6, :ll)r,3.80 (s, 4H), 3.59 (s, 2H), 2.77 - 2.72 (m, 211), 2.66 - 2.57 (m. iiH). 2.18 (s, 3H), 1.23 (t, J = 7.5, 9H); ,3CNMR: 5 157.14, 156.70, 148.60, K8.53, 137.25, 135.70, 122.59, 122.43,63.91, 60.48, 55.65, 52.11, 42.82,25.73, i 5.36. (ii) Synthesis of metal-Sigand complexes: Synthesis of Af-methyl-Ar,A',>/s/,-tns(3-metiiylpyrid'm-2-ylniethyl)eihylene-l>2-diamine iron(II)chloride.PF6 (JL2 Fe(ii)Cl]l F6). FeCl2.4H20 (51.2 mg,257 umol) was dissolved in MeOH : H20 =1:1 (2.5 mL). The solution was heated to 50 °C. Added was/V-methyl-A^^-t;is(3-[neUiylpyriJii>2-/li'nethyi)etl,iyiene-l,2-diamine (L2, 100 nig, 257 umol) in MeOH : H20 -1:1 (2.0 ml). Subsequently NaPF6 (86.4 mg, 514 (imol) in H20 (2.5 mL) was added dropwise. Cooling to room temperature, filtration and drying in vacuo (p = 0.05 mm Hg, T - room temperature) yielded the complex [L2 Fe(II)Cl]PF( (149 mg, 239 ^tinol. 93 %]■ as a yellow solid. . 'HN.MR (CD3CN, paramagnetic): £ 167.17, 142.IS, 117.01, 113.34, 104.79, 98.62, 70.77, 67.04, 66.63, 58.86, 57.56, 54.49, 51.68. 48.56, 45.90, 27.99. 27.36, 22.89, 20.57, 14.79, 12.14, 8.41, 8.16, 7.18, 6.32, 5.78, 5.07, 4.29, 3.82, 3.-0, 2.91, 2.05, 1.75, 1.58, 0.94, 0.53, -0.28, -1.25, -4.82, -18.97, -23.46. Synthesis of Ar-ethyl-Ar,A>,^-fns(3-riicttiylpyridin-2-ylrnethyl)ethylehe-lvZ-dJarnine iron(II)chJoride.PF6 ([L3 Fe(II)Cl]PF6). This synthesis was performed analogously to the synthesis for [L2 Fe(II)Cl]FF6. Starting from ;\'-ethyl-A/,;V,A^t:';s(3-me:hylpyridin-2-ylmethyl)ethylene-l,2-diamir.e (L3, 104 mg, 257 pniol) gave the complex JL3 Fe(II)Ci]PF6 (146 mg, 229 umJ, 89%) as a yellow soiid. 'HNMR(CD3CN, parfimagr.e;:c): 5 1-55.61 ;• 7.2 }J 19.23, IK.67, 92.92, 63.14, 57.44, 53.20, 50.43, 47.80, 23.59, 27.09, 22.4;-., ;..5>, 7.40, 3.63, 2."5, 2.75, 2.56, 2.26, 1.75, 1.58,0.92,0.74,-0.28,-1.63, -2.68. -KK:K -28.75. Synthesis of Ar-beuzyl-//rArt,A'-trii(3-u.CMjy;4iy- ;,iiii-2-yluieihyi).*tnylene-l,2-diamine iron(II)chloride.PF6 ([L4 Fe(U)Cl]I'Fi.). This syndesis ivas performed analogously to the synthesis for [L2 Fe(Ii)Cl]i'Ff. Sitting from /v-bcnzyl-//^V^Vl-tris(3-methylpyridin-2-ylmetliyj)€tiiylene-l,2-ci;uii;;i;ie (L4, 119.5 rr.g, 25^ pjnol) gave the complex (172 mg, 229 jimoi, 95 %) as r: yellow sclid. 'H NMR (CD3CN, paramagnetic): 6 166.33, 145.09, 119.80, 109.45, 92.94, 57.59, 52.83,47.31,28.40,27.89, 16.28, 11.05, 8.70, S.45, 7.69, 6.99, 6.01, 4.12, 2.8y, 2.71, 1.93, 1.56, -0.28, -1.68, -2.58, -11.40, -25.32. Example 4 This example describes a synthesis ;>fa CLitiiiyst :>:' bnnula (H) .vhciiin.:- (i) Synthesis ot the li^and 2J 1-diazafJ.. \z{4~.nethoxy)(2,6)pyrU'Jnophane ff4OMe)LN,H0: 4~chloro-2,6-pyridyl dimethyl ester (2). A mixture of 4-hydroxy-2,6-pyridae dicarboxylic acid (12.2 g, 60 mmoles) anu PC15 (41.3g, 200 .nmoles) in !00 ml of CC14 was refluxed until the evolution of HC1 ceased. Absolute methanol (50ml) was slowly added. After cooling, all the volatile mate.ial wai removed. The mixture was then poured into 200 nil of water and ice. Thi uiesttr crystallised immediately and was collected by filtration (70%). !H NMR (2u0MH:,, H20) 8 7.60 (2H,s), 4.05 (6H, s). 4-methoxy-2,6-pyridme dimeihanol (4). Metallic sodium (lg, 44 mmoles) was dissolved into 200 ml of dry methanol. 4-chloro-2,6pyiidyi dimethyl esier (9.2 g, 40 mmoles) was then added and the mixture was refluxed for 3 hours to obtain pure 4-methoxv-2?6-pyridyl dimethyl ester. To this solution, at R.T, NaBMi (9.1 g, 240 mmoles) was added in small portions and the mixture was refl xxed for 16 hours. Acetone (30 ml) was then added and the solution refluxed for an additional 1 hour. After ali the volatile material was removed, the residue was heated with 60 nil of a saturated NaHC03/Na2CO3 solution. After dilution with 80 ml of water, the product was continuously extracted with CHC13 for 2-3 days. Evaporation of the CHCI3 yielded 83 % of 4-methoxy-2,6- pyridine dimethanol. 'H NMR (200MHZ. H2C) 0 6.83 (2H,sj, 5.30 (2H,s), 4.-13 (4H,s), 3.82 (3H, s). 4-methox\>-2,6-dichloromethylpyridine (5), Tliis synthesis is carried out according literature. N,N'-ditosyl-2.11 -diqza(3.3 J-Q'-'"^thgx^2^o}^lfJ!jTn[)ha^ the procedure is similar to that described in the literature. The crude product obtained is practically pure (yield=95%.) IH-NMR (CDCI3, 250 iMHz): 7.72 (4H, d, J- 7Rz), 7.4 (1H, 1, J= 6Hz), 7,35 (4H, d, J= 7Hz), 7.1 (1H, d, J= 6Hz), 6.57 (21-1, s), -i.-:5 ;-Ti, s), 4.35 (4ii, s), 3.65 (311, s), 2.4 (6H s). 2. lJ-diazaf3.31-(4-methoxy)(2: djeyridinopna/ie. The procedure is similar to the one described previously. The crude product obtaineu is purified by chromatography (alumina, CH2Cl2/MeOH 95:5), yield = 65%. "H-NMR (CDCI3, 250 MHz): 7.15 (1H, t, j- 6H:■.), 6.i5 (1H, d, J= (5Hz), 6.05 (2H, s), 3.95 (4H, s), 3.87 (4H, s), 3.65 (3R s). Mass spectrum (El): M+ = 270 (100%) Hi) Synthesis of the complex [FeHOMeLNjH-OCblCl: 270 mg of 2,1 l-d:aza[3.3]-(4-;i.etho. Ci5Hi8N4Cl3OFe-0,5MeOH (found/theoretical): C =41.5/41.61 rM.46/4.52 N=12.S/12.08 IR(KBrpellets, cm-J): 3545, 3414, 3235, 3075,2883,1615, 1477, !437, 1340,1157, 1049,883,628,338. V Example 5: This example describes a synthesis of a catalyst of formula (H) wherein:- !■ H--N N' N-H in FeCk (CT) R,-Rg=H; x=l; y=l; z=l; X=Cl, n=2; Y-C1\ p-i Synthesis of the complex IFcfLN^JCh.iO: 240 mg of LN4H2 (1 rnmoles) were dissolv -id in : 5 ml of dry THF. To this solution was added a solution of 270 mg of FeC^^FbQ {1 nnv.oh) in 5 ml of McOH. The resulting mixture is stirred and gives spontaneously 340 n\ ■> of yellow powdc;, yield = 85%. IR (KBr peliets, Cin'1): 3445, 30.31, 2851,1629, 1062, 1473, 1427, 1335, 1157, 1118, 1045,936,796,340,313 Example 6: This Example describes a, synthesis of a catalyst of formula (H) wherein:- 5^ Ri=R2=Rs.g=H; RH^=Me; x-1; y=l; n-2; z=i; X=F; m=2; Y=PF;; p=l difIuoro[N,N'dinieih\l-2Jl-diuzaf3.31(2,6: py.diii-tODhanelman°antse(W) hexafluorophosph ate. (i) Synthesis of the..ligand N,N'dimzthyi~i: J i-di(:znf3.3l(2,6)vwidinoDhane: 2,6-dichloromethvlvvridine. A mixture of 2,6-dimethanolpyridine (5z, 36 mmoles) and 75 ml of SOC12 was refluxed ibr 4 hours. '\ he mixture was concentrated (half volume). Toluene was added (50 tr.1). The solid t riv:?'.1 after cooling W:LV then filtered and dissolved in water and the solution neutralised v/ith NaHC03. The solid obtained is filtered and dried (65%). 'H NMR (2C0MHZ, CDCI3) 5 7.8 (lH,t,JJ-7Hz), 7.45 (2H,d, J=7 Hz), 4.7 (4H, s). Sodium p-loluenesulphonamidure. To a mixture of Na° |.n dry EtOH (0.7 g, 29 mmoles) was added/MoluenesuIphonamide (5 g, 29 mmoles) and the solution was refluxed for 2 hours. After cooling, the solid obtained was filtered, washed with EtOH and dried (quantitative yield). N.N'-'ditosvl-2,l]-digza[3.3](2.6)pvridinophane. To a solution of sodium p-toluenesulphonamiduxe (1.93 g, 10 mmoles) in 200 ml of dry DMF at 80°C was slowly added 2,6-dichloromethy!pyridir;': (1.76 g. 10 ma-ioSes). After 1 hour a new portion of sodium p-toluenesulphonamidure v/as addec (1.93 g) and the final mixture stirred at 80°C for an addition 4 hours. The solution \va:: then evaporated to dryness. The solid obtained was washed with water and ih.n wiiri EtOH and finally crystallised in an CHCl3/MeOH mixture. The solid obtained I: i'iitered and dried. The yield of (.15) was 55 %. 'H NMR. (200MHZ, CDCh) 5 7.VS (4H.d, J=6Hz), 7.45 .'6H,m),' 7.15 ( 4H,d, J=6Hz), 4.4 (8H, s), 2.4 (6H,s) 2.1l-diaza[3.31(2.5)pyridinop,ian (2,6)pyridinophane (1.53 g, 2.Is rnmoles) a.id ; for 2 hours. The solution, cooled and diluted with 14 ml of water, was then carefully poured into a saturated NaOH solution. T:.e ;oiid formed is extracted with chloroform. The organic layer is evapo/aio-j to dryness to yield 85 % of 2,ll-diaza[3.3](2,6)pyridinophare. 'H NMR (200MHz, CDCh) S 7.1 (2H,t, J=7Hz), 6.5 (4H,d, J=7 Hz), 3.9 (8H, s). N. N'-dimethyl-2,1J-diaza[3.3 ](2,6)pyridinoption-:. A mixture of 2,1 !-diaza[3.3] (2,6)pyridinophane (0.57 g, 2.4 mmolei), 12u ml of fonnic acid and 32 ml of formaldehyde (32% in water) was rciluxed for 2-> hours. Concentxa;ed HC1 (10 ml).were added and the solution evapo:a!ed to ary.ias. : he solid was dissolved in water and basified with NaOH 5M, and the resulting .-olutiun vvas extracted with CriC!v The solid obtained was purif.ed by chromatography en a!o.\ (CH2Cl-,+l% MeOH) to yield 51 % of N,N,-dimethyl-2,ll-diaza[3.3](2,6)pyridinophr1jie. 'H NMR (200MHz, CDC13) 6 7.15 (2H,t, J=7Hz), 6.8 (4H,d, J=7 Hz), 3.9 (8H, s), 2.73 (6H,s). (ii) Synthesis of the complex: MnF3 (41.8 mg, 373 rnmoles) was dissolved in 5 ml of MeOH, and N,N'-dimethyl~2,U-diaza[3.3](2,6)pyridinophane (0.1 g, 373 nimoles) wa3 added with 5 ml of THF. After 30 minutes of stirring at RT, 4 ml of THF saturated in NBu4PF6 were added, and the solution left without stining until the crystallisation was finished. The product was collected by filtration to yield 80% of comj:!e.\. Elemental analysis (found, theoretical): %C (38.35, 37.94), %N (11.32, 11.1), %ll (J.75, 3.95). IR (KB: pellet, cm"1): 3086, 2965,2930,2821, 1607, 1478, 1444, 1425, 1174, 1034, 1019, 844, 796, 603, 574, 555. UV-Vis (CH3CN, X in run, ty. 500, 110; J-.50, 3t: (CH3CN/H;0:1.1, X in nm, ey. 465, 168; 850, 30. Example 7: Bleaching of tomato-oil stained cloth.1: without and vyjch addition of IFefMeWPvVCHiCKUfCIOjV. immediately a;>er (he wash (t=0) and after 24 h storage (t=l day). In an aqueous solution containing 10 mM carl-onate buffer (pH 10) without and with 0.6 g/1 LAS (linear alkylbenzene sulphonate) or containing '-. 0 mM borate buffer (pH 8) without and with 0.6 g/1 LAS, tomato-soya oil stained cloth.-; (6x6 cm) were added and stirred for 30 minutes at 30 °C. m a second series of expei-iments, the same tes.s wen- done in the presence of 10 pivl [Fe(MeN4PyXCi-I3CN)j(C;04;:».. referred to in the table below as Fe(MeN4Py). After the wash, the cloths were dried in a tumble drier and the reflectance was measured with a Minolta 3700d spectrophotometer at 460 run. The dilTerence in reflectance before and after the wash is defined as AR460 value. The cloths were measured immediately after the wash (t=0), and after 24 h storage in a dark room under ambient conditions (t=l d). The results obtained are listed in ihe table below: AR value (t=0) blank (no cat) AR value (M)) + Fe(N';eN4i'y) AR value (t= Id) blank AR value (t= Id) + Fe(MeN4Py) pH 8 no LAS 11.5 23 11.5 44 pH 8 with LAS 12.5 19 12.5 36 pH 10 no LAS 10.5 30 pH 10 with LAS 12.5 30 A clear bleaching effect can thus be obs:-i,oc nil:? the treated fabric cloths were dried and stored. Example 8: Bleaching of tomaio-oil stained cloths v/i.:hout :s,d with addition of various metal catalysts measured after 24 hours storage in the park under ambient conditions. In an aqueous solution containing 10 mM carbonate buffer (pH 10) without and with 0.6 g/1 LAS (linear alkylbenzene sulphonate) or containing 10 mM borate buffer (pH 8) without and with 0.6 g/1 LAS, tomato-sin;: o'.i .<:.lined cloths were added a kept in contact with the solution under agitation for minutes at comparative experiments same done bv addition of p.m dinuclear or pm mononuclear complex referred to lie tab:.- below.> After the wash, the cloths were rinsed v, ith v- j.;c and subsequently dried at 30 °C and the change in colour was measured after ka\ uiv ric cloths for 24 h in the dark with a Linotype-Hell scanner (ex Linotype). The change in colour (including bleaching) is expressed as the AE value. The measured colour difference (AE) between the washed cloth and the unwashed cloth is defined as follows: V wherein AL is a measure for the difference in darkness between the washed and unwashed test cloth; Aa and Ab are measures for the difference in redness and yellowness respectively between bodi cloths. Witn regard to this colour measurement technique, reference is made to Commission International de l'Eclairage (C1E); Recommendation on Uniform Colour Spaces, ouiour difference equations, psychometric colour terms, supplement no 2 to ClE Publication, no 15, Colcrmeiry, Bureau Centra] de la CfE, Paris 1978. The following complexes were used: i) [Mn2(l,4,7-trimethyl-l,4,7-taaz.-.cycl-MiO!;ane)2(M-0)3](PF«)2 (1) Synthesised according so EP~B~i.56357; ii) [Mn(LN4Me2)3 (=difiuorofN>N,dir:ieihy!-2,n-diaza[3.3](2,6)pyridinophane] manganese(III)hexafluorophosphate) (2) Synthesised as described previously: iii) [Fe(OMe)LN4H2)C!2] (=Fe(2,l l-diaz:i[3.3]-(4-methoxy)(2,5)pyridinophane)Cl2 Synthesised as described previously; iv) C12-CoCo (!) Synthesised according tu EP-A-403.'3. ; v) Me2CoCo (3) Synthesised according to EP-A-40813i; vi) [Fe(tpen)](CI04)2 (6) Syfithesiscd according to WO-A-9748787; vii) [Fe(N,N,N,-lxis(pyridin-2ylmethyi)-N-n';eihyl-1 ^-ethylenediamine)Cl](PFc)2 (7) Synthesised according to I. Bernal, et a!., J. Chem. Soc, Dalion Trans, 22, 3667 (1995): gave 0.093g of complex (23% yield). xiii) [Mn2(N,N,N N'-tetrakis(pyriclin-2-yln,.et;iyi ,-propan-1,3HJiamine)(u-OXu-OAc)2](C104)2 (U) w Synthesized as follows: To a stirred solution of 6.56 g 2-chlorc -m jthylpyridine (40 mmol) and OJ75 ml 1,3-propanediamine (9 mmol) in 40 ml water, i: added slowly at 70'C over a period of 10 minutes, 8 ml 10M NaOH-solution. The colour of the reaction turned from yellow to deep red. The reaction was stirred for an additional 30 minutes at 70°«C, after which the reaction was cooled to room temperature The reaction mixture was extracted with dichloromethane (totally 200 ml), after which the red organic layer was dried over MgS04, filtered and evaporated under reduced pressure, to yield 4.51 g of -i red/brown oil. After scratching the bottom with a spatula ine residue turned solid, trying to purify .» the crude product by washing it with water tne product became messy, so immediately the purification was stopped and dried with ether. A sample was taken to analyse the product by NMR, while the rest was immediately reacted with Mn(OAc)3 (see complexation). 'H-NMR (400MHz) (CDCI3); d (ppm): 1.65 (q-5, propane-A, 2H), 2.40 (t, propane-B, 4H), 3.60 (s, N-CHrpyr, 8H);6.95 (t, pyr-H4, 4H). 7.30 (d, pyr-H3; 4H), 7.45 (t, pyr-H5,4H), 8.35 (d, pyr-H6, 4H). To a stirred solution of 4.51 g TP17-I (0.0 i 03 rnol) in 40 ml methanol is added at room temperature (22JC) 2.76 g Mn(OAc;3 (Q.ol03 mol) . The colour 01' the reaction turned from orange to dark brown, after die addition the mixture was stirred for 30 minutes at room temperature and filtered. To the filtrate was added at room temperature 1.44 g NaCIO* (0.0103 mmol) and the reaction mixture was stirred for another hour, filtered and nitrogen dried, yielding 0.73 g bright brown crystals (8%). 'H-NMR (400Mhz) (CD3CN); d (ppm): -42.66 (s), -15.43 (s), -4.8 (s, br.), 0-10 (m, br.), 13.81 (s), 45.82 (s), 49.28 (s), 60 (s, br.), 79 (s, br.), 96 (s, br/; IR/fcrn'1): 3426, 1608 (OC), 1563 (ON), 1487 , 1430 (C-H), 1090 (C10 767,623. UV/Vis (X, nm(e, l-mor'-cm"1): 260 (2.4 xlO4), 290 (sh), 370 (sh), 490 (5.1 xlO2), 530 (sh; 3.4 xlO2), 567 (sh), 715 (1.4 x 102). Mass spectrum: (ESP+) m/z 782 [TPTN Mn(]I)Mn(lII) (y-OH) (p-OAc)2 (C104y]* ESR (CH3CN): The complex is ESR silen; supporting the presence of a Mn(IlI)Mn(IH) species. Elemental analysis: found (expected for Mr^Coi .-Jj8N60i4Cb (MW!=899): C 41.14 (41.4), H 4.1 (4.2), N 9.23 (9.34), O 24.8 (24.9), CI 7.72 (7.9), Mn 12.1 (12.2). xiv) [Mn2(tpa>2(p--0)2](PF6)3 (14) Synthesised according to D.K. Towle, C.,\. Boisford, D.J. Hodgson, 1CA, 141, 167 (1988); xv) [Fe(N4Py)(CH3CN)](C104)2 (15) Synthesised according to WO-A-9534628: xvi) [Fe(MeN4Py)(CH3CN)](C10,)2 (16) Synthesised according to EP-A-0909809. xvii) [Mn2(2,6-bis{(bis(2-pyridylmethyl)arnino)!nethylj-4-methylphenol)XM-OAc)j])( Synthesised according to H. Diril et al., J.Am.Chem.Soc, 111, 5102 (1989); xviii) [Mn2(N,N,NrN'-tetrakisCoenzimidazoi-2-yiinethyl)-propan-2-olate-1,3-diamine)] Oi-OAc)2](C104)2(lS) Synthesised according to P. Marthur et al., J.Am.Chem.Soc, 109, 5227 (1937). Results: 5 Table: bleach activity on Tomato Oil stains .tx?re\;si J in .iE values obtained for various metal complexes measured after 24 h. BL * 1 2 3 4 5 6 7 3 9 10 pHS -LAS ° 1 1 2 2 4 J 9 2 9 4 2 7 pHS ■HAS 2 6 7 7 2 16 i 19 19 2 10 pHlO -LAS 1 1 3 3 9 j 17 ! 2 4 9 2 2 pHIO +LAS 3 16 14 14 4 | i ii ; i 6 11 4 _..,..! 4 ** 2 2 6 20 19 -1 4- 1 21 C 5 7 6 20 20 3 2 23 2 5 4 19 IS 3 8 21 17 7 * 7 19 20 11 c 21 *>- BL: Reference: no catalyst added, only buffer vith and without LAS 10 ** Compound 16 with 10 mM hydro;;-'- peroxide Performing the experiment under argon (comjxjund J 6 ai pH 10 with LAS) showed that the bleaching effect upon storage is absent, thus show::;g that dioxygen i:; involved in the bleaching process. WE CLAIM: 1. A method of treating a textile by contacting the textile with an organic substance which forms a complex with a transition metal, the treatment providing the organic substance in a form that is substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system whereby the complex catalyses bleaching of the textile by atmospheric oxygen after the treatment, wherein the treated textile is dried and bleaching is catalysed on the dry textile. 2. A method as claimed in claim 1, wherein the treatment comprises contacting the textile with the organic substance in dry form. 3. A method as claimed in claim 1, wherein the treatment comprises contacting the textile with a liquor containing the organic substance and then drying. 4. A method as claimed in claim 3, wherein the liquor is an aqueous liquor. 5. A method as claimed in claim 4, wherein the liquor is a spray-on fabric treatment fluid. 6. A method as claimed in claim 4, wherein the liquor is a wash liquor for laundry cleaning. 7. A method as claimed in claim 3, wherein the liquor is a non-aqueous liquor. 8. A method as claimed in claim 7, wherein the liquor is a dry cleaning fluid. 9. A method as claimed in claim 7, wherein the liquor is a spray-on aerosol fluid. 10. A method as claimed in claim 3, wherein the medium has a pH value in the range from pH 6 to 11. 11. A method as claimed in claim 10, wherein the liquor has a pH value in the range from pH value in the range from pH 8 to 10. 12. A method as claimed in any of claims 3 to 11, wherein the liquor is substantially devoid of a transition metal sequestrant. 13. A method as claimed in any of claims 3 to 12, wherein the liquor further comprises a surfactant. 14. A method as claimed in any of claims 3 to 13, wherein the liquor further comprises a builder. 15. A method as claimed in any of claims 1 to 14, wherein the organic substance comprises a preformed complex of a ligand and a transition metal. 16. A method as claimed in any of claims 3 to 14, wherein the organic substance comprises a free ligand that complexes with a transition metal present in the liquor. 17. A method as claimed in any of claims 4 to 14, wherein the organic substance comprises a free ligand that complexes with a transition metal present in the textile. 18. A method as claimed in any of claims 1 to 14, wherein the organic substance comprises a composition of a free ligand or a transition metal-substitutable metal-ligand complex, and a source or transition metal. 19. A method as claimed in any of claims 1 to 18, wherein the organic substance forms a complex of the general formula (A1): [MaLkXn]Ym (Al) in which: M represents a metal selected from Mn (II)- (III)- (IV)- (V), Cu (l)-(ll)-(lll), Fe (l)-(ll)-(lll)-(IV),Ni (l)-(ll)-(lll), Cr (ll)-(lll)-(IV)-(V)-(VI)-(VII), Ti (ll)-(||l)-(ll)-(lll)-(IV), V (ll)-(lll)-(IV)-(V), Mo (ll)-(lll)-(IV)-(V)-(VI). W (IV)- (V)- (VI), Pd (II), Ru (II)-(lll)-(IV)-(V) and Ag (l)-(ll); L represents a ligand, or its protonated or deprotonated analogue: X represents a coordinating species selected from any mono, bi or tri charged anions and any neutral molecules able to coordinate the metal in a mono, bi or tridentate manner; y represents any non-coordinated counter ion; a represents an integer from 1 to 10; k represents an integer from 1 to 10; n represents zero or an integer from 1 to 10; and m represents zero or an integer from 1 to 20. A method as claimed claim 19, wherein in formula (A1): X represents a coordinating species selected from 02', RB022-, RCOO-, RCONR", OH-, N03-, NO2-, NO, CO, CN-, S2-, RS-, P034-, STP-derived anions, PO3OR3", H20, C032-, HC03-, ROH, NRR'R", RCN, CI-, Bi, OCN-, SCN-, CN, N3-, F-, I-, RO-, CIO4-, So42-, HSO4-, S032- and RSO3-; and Y represents a counter ion selected from CIO4-, BR4-, [FeCI4]", PF6", RCOO", NO3-, NO2-, RO-, NWR'-R'", CI-, Br-, F-, I-, RSO3-, S2062', OCN-, SCN-, Li+, Ba2+, Na+, Mg2+, K+, Ca2+, Cs+, PR4\ RB022", S042", HS04-, SO32", SbCU", CuCU2", CN, P043~, HPO42", H2P04", STP-derived anions, C032", HC03 and BF4", wherein R, R', R", R'" independently represent a group selected from hydrogen, hydroxyl, -OR (wherein R=alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl heteroaryl or carbonyl, derivative group), -Oar, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl heteroaryl and carbonyl derivative groups, each of R, Ar, alkyl, alkenyl, cycloalkyi, heterocycloalkyi, aryl, heteroaryl and carbonyl derivative groups being optionally substituted by one or more functional groups E, or R6 togther with R7 and independently R8 together with R9 represent oxygen; E is selected from functional groups containing oxygen, sulphur, phosphorus, nitrogen, selenium, helogens, and any electron donating and/or withdrawing groups. A method as claimed in claim 19 or claim 20, wherein in formula (A1): M represents a metal selected from Mn (II)- (III)- (IV)- (V), Cu (l)-(ll), Fe (II)-(III)-(IV) and Co (I)-(II)-(III); X represents a coordinating species selected from O2", RB022", RCOO-, OH-, NOV, N02", NO, CO, CN-, S2", RS-, P034". H20, C032", HC03", ROH, NRR'R", CI-, Bi, OCN-, SCN-, RCN, N3-, F-, I-, RO-, CIOY, S042", HS04\ S032_ and RS03~; Y represents a counter ion selected from CI04", BR4", [FeCI4]\ PF6", RCOO-, N03-, NO2-, R0-, N+RR'R"R"', CI-, Br-, F-, I-, RS03-, S2062, OCN-, SCN-, Li+, Ba2+, Na+, Mg2+, K+, Ca2+, PR4+, S042", HS04", SO32" and BF4", wherein R, R', R", R'" represent represent hydrogen, optionally substituted alkyl or optionally substituted aryl; a represents an integer from 1 to 4; k represents an integer from 1 to 10; n represents zero or an integer from 1 to 4; and m represents zero or an integer from 1 to 8. A method as claimed in any of claims 19 to 21, wherein L represents a ligand of the general formula (BI): wherein g represents zero or an integer from 1 to 6; r represents an integer from 1 to 6; s represents zero or an integer from 1 to 6; Z1 and Z2 independently represent a heteroatom or a heterocyclic or hateroaromatic ring, Z1 and/or Z2 being optionally substituted by one or more functional groups E as defined below; Q1 and Q2 independently represent a group of the formula: R6 R8 -[- C-k-[-Yl-]e-( C-]r R7 RO wherein 10>d+e+f>1; d=0-9; e=0-9; f=0-9; each Y1 is independently selected from-0-,-S-,-SO-,-S02-,- (G') N-,- (G') (G2) N- (wherein G1 and G2 are as defined below),-C (0)-, arylene, alkylene, heteroarylene,-P- and -P (O)-; if s>1, each-[-Z1(R1)-(Q1)r-]-group is independently defined; Rl, R2, R6, R7, R8, R9 independently represent a group selected from hydrogen, hydroxyl, -OR (wherein R= alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or carbonyl derivative group), -OAr, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and carbonyl derivative groups, each of R, Ar, alkyl, alkenyl, cycloalkyi, heterocycloalkyi, aryl, heteroaryl and carbonyl derivative groups being optionally substituted by one or more functional groups E, or R6 together with R7 and independently R8 together with R9 represent oxygen; E is selected from functional groups containing oxygen, sulphur, phosphorus, nitrogen, selenium, halogens, and any electron donating and/or withdrawing groups (preferably E is selected from hydroxy, mono-or polycarboxylate derivatives, aryl, heteroaryl, sulphonate, thiol (-RSH), thioethers (-R-S-R1), disulphides (-RSSR'), dithiolenes, mono-or polyphosphonates, mono-or polyphosphates, electron donating groups and electron withdrawing groups, and groups of formulae (C) (G2) N-, (G") (G2) (G3) N-, (G') (G2) N-C (O)-, G30-and G3C (O)-, wherein each of G1, G2 and G3 is independently selected from hydrogen, alkyl, electron donating groups and electron withdrawing groups (in addition to any amongst the foregoing)); or one of R1-R9 is a bridging group bound to another moiety of the same general formula; T1 and T2 independently represent groups R4 and R5, wherein R4 and R5 are as defined for R1-R9, and if g=0 and s>0, R1 together with R4, and/or R2 together with R5, may optionally independently represent =CH-RIO, wherein RIO is as defined for R1-R9, or T1 and T2 may together (-T2-TI-) represent a covalent bond linkage when s>l and g>0; if Z1 and/or Z2 represent N and T1 and T2 together represent a single bond linkage and R1 and/or R2 are absent, Q1 and/or Q2 may independently represent a group of the formula: =CH- [-Y1-]e-CH=, optionally any two or more of R1, R2, R6, R7, R8, R9 independently are linked together by a covalent bond; if Z1 and/or Z2 represents O, then Rl and/or R2 do not exist; if Z1 and/or Z2 represents S, N, P, B or Si then R1 and/or R2 may be absent; if Z1 and/or Z2 represents a heteroatom substituted by a functional group E then Rl and/or R2 and/or R4 and/or R5 may be absent. A method as claimed in claim 22, wherein Z1 and Z2 independently represent an optionally substituted heteroatom selected from N, P, O, S, B and Si or an optionally substituted heterocyclic ring or an oiptionally substituted heteroaromatic ring selected from pyridine, pyrimidines, pyrazine, pyramidine, pyrazole, pyrrole, imidacole, benzimidazole, quinoleine, isoquinoline, carbazole, indole, isoindole, furane, thiophene, oxazole and thiazole. A method as claimed in claim 22 or claim 23, wherein R1-R9 are independently selected from-H, hydroxy-C0-C2o-alkyl, halo-Cc-C20-alkyl, nitroso. formyl-C0-C2o-alkyl, carboxyl-C0-C20-alkyl and esters and salts thereof, carbamoyl-C0-C2o-alkyl, sulpho-Co- C20-alkyl and esters and salts thereof, sulphamoyl-C0-C2o-alkyl, amino-C0-C2o-alkyl, aryl-Co-C2o-alkyl, heteroaryl-C0-C2o-alkyl, C0-C20-alkyl, alkoxy-Co-Cs-alkyl, carbonyl- C0-C6-alkoxy, and aryl-C0-C6-alkyl and C0-C2o-alkylamide; or one of R1-R9 is a bridging group -Cn, (R11) (R12)-(D) p-Cm (Rl I) (R12)-bound to another moiety of the same general formula, wherein p is zero or one, D is selected from a heteroatom or a heteroatom-containing group, or is part of an aromatic or saturated homonuclear and heteronuclear ring, n' is an integer from 1 to 4, m' is an integer from 1 to 4, with the proviso that n'+m' 25. A method as claimed in any of claims 22 to 24, wherein T1 and T2 together form a single bond linkage and s>1, according to general formula (Bll): wherein Z3 independently represents a group as defined for Z1 or Z2; R3 independently represents a group as defined for R1-R9; Q3 independently represents a group as defined for Q1, Q2; h represents zero or an integer from 1 to 6; and s' = s-1. 26. A method as claimed in claim 25, wherein in general formula (Bll), s'=1, 2 or 3; e=f=o; R6=R7=H. 27. A method as claimed in claim 26, wherein the ligand has a general formula selected from: 28. A method as claimed to claim 27, wherein the ligand has a general formula selected from: 29. A method as claimed in claim 28, wherein R1, R2, R3 and R4 are independently selected from -H, alkyl, heteroaryl, or represents a bridging group bound to another moiety of the same general formula with the bridging group being alkylene or hydroxy-alkylene or a heteroaryl-containing bridge. 30. A method as claimed in claim 29, wherein R1, R2, R3 and R4 are independently selected from -H, methyl, ethyl, isopropyl, nitrogen-containing heteroaryl, or a bridging group bound to another moiety of the same general formula with the bridging group being alkylene or hydroxy-alkylene. 31. A method as claimed in any of claims 26 to 30, wherein in the complex M= Mn (II)- (IV), Cu (I) - (III), Fe (ll)-(lll) , Co (II)- (III); X= CH3CN, OH2, CI-, Br, OCN-, N3", SCN-, OH-, , O2", P043", C6H5B022", RCOO' ; Y= CLCV, BPH4", Br-, CI-, [FeCI4]",PF6-,N03"; a=1,2,3,4; n= 0,1,2,3,4,5,6,7,8,9; m= 1,2, 3, 4; and k= 1,2,4. 32. A method as claimed in claim 25, wherein in general formula (Bll), s' = 2; r=g=h=l; d=f=o; e=1; and each Y1 is independently alkylene or heteroarylene. 33. A method as claimed in claim 32, wherein the ligand has the general formula: wherein Ai, A2, A3, A4 are independently selected from C1-9" alkylene or heteroarylene groups; and NL and N2 independently represent a hetero atom or a heteroarylene group. 34. A method as claimed in claim 33, wherein NT represents an aliphatic nitrogen N2 represents a heteroarylene group; R1, R2, R3, R4 each independently represent -H, alkyl, aryl or heteroaryl; and Ai, A2i A3, A4 each represent -CH3-. 35. A method as claimed in claim 34, wherein the ligand has the general formula: wherein R1, R2 each independently represent -H, alkyl, aryl or heteroaryl. 36. A method as claimed in any of claims 32 to 35, wherein in the complex [MaLkXn] Ym: M= Fe (II)- (III), Mn (II)- (IV), Cu (II), Co (ll)-(lll) ; X= CH3CN, OH2, CI-, Br-, OCN-, N3-, SCN-, OH-, O2", P043", C6H5B022", RCOO' ; Y= CIO4", BPh4", Br-,CI-, [FeCI4]-, PF6\ N03"; a=1,2, 3, 4; n=0,1,2, 3,4, 5,6, 7, 8, 9; m= 1, 2, 3, 4; and k=1,2, 4. 37. A method as claimed in claim 25, wherein in general formula (Bll), s'=2 and r=q=h=l, accordinq to the qeneral formula: 38. A method as claimed in claim 37, wherein ZI=Z2=Z3=Z4=a heteroaromatic ring; e=f=0; d=1; and R7 is absent. 39. A method as claimed in claim 37, wherein Z1-Z4 each represent N; R1-R4 are absent; both Q 1 and Q3 represent =CH-[ -YI-] e-CH=; and both Q2 and Q4 represent -CH2- [-YI-]n-CH2-. 40. A method as claimed in claim 39, wherein the ligand has the general formula: A- wherein A represents optionally substituted alkylene optionally interrupted by a heteroatom; and n is zero or an integer from 1 to 5. 41. A method as claimed in claim 40 wherein RI-R6 represent hydrogen, n=l and A= -CH2. CHOH-, -CH2N(R)CH2- or -CH2CH2N(R)CH2CH2- whereinRrepresents hydrogen or alkyl. 42. A method as claimed in claim 41, wherein A=-CH2-.-CHOH- or -CH2CH2NHCH2CH2-. 43. A method as claimed in any of claims 37 to 42 wherein in the complex [MaLkXn]Ym: M= Mn (II)- (IV), Co (II)- (III), Fe (ll)-(lll) ; X= CH3CN, OH2, CI-, Br, OCN-, N3-, SCN-, OH-, , 02', P043", C6H5B022-, RCOO' Y= CI04", BPh4-, Br-, CI-, [FeCU]-, PF6-, N03"; a=1,2,3,4; n= 0,1,2,3,4,5,6,7,8,9; m= 1, 2, 3, 4; and k=1,2,4. 44. A method as claimed in any of claims 22 to 24, wherein T1 and T2 independently represent groups R4, R5 as defined for R1-R9. according to the general formula (Bill): 45. A method as claimed in claim 44, wherein in general formula (Bill), s=1; r=l; g=0; d=f=1; e=1-4; YI=-CH2-; and R1 together with R4, and/or R2 together with R5, independently represent =CH-R10, wherein R10 is as defined for R1-R9. 46. A method as claimed in claim 45, wherein R2 together with R5 represents =CH-R10. 47. A method as claimed in claim 45 or claim 46, wherein the ligand is selected from: R5 R3 R1 R4 R1 R4 48. A method as claimed in claim 47, wherein the ligand is selected from: wherein R 1 and R2 are selected from optionally substituted phenols, heteroaryl-C0-C20- alkyls, R3 and R4 are selected from-H, alkyl, aryl, optionally substituted phenols, heteroaryl-Co-C2o-alkyls, alkylaryl, aminoalkyl, alkoxy. 49. A method as claimed in claim 48 wherein R1 and R2 are selected from optionally substituted phenols, heteroaryl-C0-C2-alkyls, R3 and R4 are selected from-H, alkyl, aryl, optionally substituted phenols, nitrogen-heteroaryl-C0-C2-alkyls. 50. A method as claimed in any of claims 45 to 49 wherein in the complex [MaLkXn]Ym: M= Mn (II)- (IV), Co (II)- (III), Fe (ll)-(lll); X= CH3CN, OH2, CI-, Br-, OCN-, N3", SCN-, OH-, O2-, P043",C6H5B022", RCOO' ; Y- CI04", BPh4", Br-, CI-, [FeCI4]-,PF6-,N03-; 3=1,2,3,4; n=0, 1,2, 3, 4, 5, 6, 7, 8, 9; m=1, 2, 3, 4; and k= 1.2,4. 51. A method as claimed in claim 44, wherein in general formula (Bill), s=1; r=1; g=0; d=f=1; e=1-4; Y1=-C (R') (R"), wherein R' and R" are independently as defined for R1-R9. 52. A method as claimed in claim 51, wherein the ligand has the general formula: 53. A method as claimed in claim 52, wherein R1, R2, R3, R4, R5 are-H or C0-C2o-alkyl, n=0 or 1, R6 is-H, alkyl,-OH or-SH, and R7, R8, R9, R10 are each independently selected from-H, Co-C2o-alkyl, heteroaryl-Co-C20-alkyl, alkoxy-C0-C8- alkyl and amino-Co-C2o- alkyl. 54. A method as claimed in any of claims 51 to 53 wherein in the complex [MaLkXn]Ym: M= Mn (II)- (IV), Fe (II)- (III), Cu (II), Co (ll)-(lll); X= CH3CN, OH2, CI-, Br-, OCN", N3-, SCN-, OH-, O2" P043",C6H5B022-, RCOO- Y= CIO4 BPh4-, Br-, CI-, [FeCI4]-, PF6-, N03-; a= 1,2, 3,4; n=0, 1,2, 3,4; m=0, 1, 2, 3,4, 5,6, 7, 8; and k= 1,2, 3,4. 55. A method as claimed in claim 44, wherein in general formula (BUI), s=0; g=1 ; d=e=0; f=1-4. 56. A method as claimed in claim 55, wherein the ligand has the general formula: 57. A method as claimed in claim 56, with the proviso that none of R1 to R3 represents hydrogen. 58. A method as claimed in claim 56 or claim 57, wherein the ligand has the general formula: wherein R1, R2, R3 are as defined for R2, R4, R5. 59. A method as claimed in any of claims 55 to 58, wherein in the complex [MaLkXn]Ym M= Mn (II)- (IV), Fe (II)- (III), Cu (II), Co (II)- (III); X= CH3CN, 0H2> CI', Br', OCN', N3\ SCN', OH', 02', P043', C6H5B022', RCOO-; Y= CIO4-, BPh4-, Br-, CI, [FeCI4]-, PF6-, N03-; a= 1,2, 3,4; n=0, 1,2, 3,4; 171=0,1, 2, 3,4, 5,6, 7, 8; and k= 1,2, 3,4. 60. A method according to any of claims 19 to 24, wherein L represents a pentadentate ligand of the general formula (B): wherein each R1, R2 independently represents-R4-R5 R3 represents hydrogen, optionally substituted alkyl, aryl or arylalkyl, or-R4-R5, each R4 independently represents a single bond or optionally substituted alkylene, alkenylene, oxyalkylene, aminoalkylene, alkylene ether, carboxylic ester or carboxylic amide, and each R5 independently represents an optionally N-substituted aminoalkyl group or an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl. 61. A method as claimed in claim 60, with the proviso that R3 does not represent hydrogen. 62. A method as claimed in any of claims 19 to 24, wherein L represents a pentadentate or hexadentate ligand of the general formula (C): R1R1N-W-NR1R2 wherein each R1 independently represents-R3-V, in which R3 represents optionally substituted alkylene, alkenylene, oxyalkylene, aminoalkylene or alkylene ether, and V represents an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl; W represents an optionally substituted alkylene bridging group selected from -CH2CH2-rCH2CH2CH2-rCn2Cn2CH2CH2-,-CH2-C6H4-CH2-,-CH2-C6Hio-CH2-, and-CH2-CioH6-CH2-; and R2 represents a group selected from R1, and alkyl, aryl and arylalkyl groups optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulphonate, amine, alkylamine and N+(R4)3, wherein R4 is selected from hydrogen, alkanyl, alkenyl, arylalkanyl. arylalkenyl, oxyalkanyl, oxyalkenyl, aminoalkanyl, aminoalkenyl, alkanyl ether and alkenyl ether. A method as claimed in any of claims 19 to 24, wherein L represents a macrocyclic ligand of formula (E): wherein Z1and Z2 are independently selected from monocyclic or polycyclic aromatic ring structures optionally containing one or more heteroatoms, each aromatic ring structure being substituted by one or more substituents; Y1 and Y2 are independently selected from C, N, O, Si, P and S atoms; A1 and A2 are independently selected from hydrogen, alkyl, alkenyl and cycloalkyl (each of alkyl, alkenyl and cycloalkyl) being optionally substituted by one or more groups selected from hydroxy, aryl, heteroaryl, sulphonate, phosphate, electron donating groups and electron withdrawing groups, and groups of formulae (G1)(G2) N-, G3OC (O)-, G30- and G3C (0)-, wherein each of G1, G2 and G3 is independently selected from hydrogen and alkyl, and electron donating and/or withdrawing groups (in addition to any amongst the foregoing); i and j are selected from 0,1 and 2 to complete the valency of the groups Y1 and Y2; each of Q1-Q4 is independently selected from groups of formula wherein 10>a+b+c+d>2; each Y3 is independently selected from-0-,-S-,-SO-,-S02-,-(G1) (G2) N-,- (G1) N-(wherein G1 and G2 are as hereinbefore defined),-C (O)-, aryl, heteroaryl,-P-and -P(O)-, each of A3-A6 is independently selected from the groups hereinbefore defined for A1and A2; and wherein any two or more of A1-A6 together form a bridging group, provided that if A1 and A2 are linked without simultaneous linking also to any of A3-A6, then the bridging group linking A1and A2 must contain at least one carbonyl group. Dated this 1st day of March 2001 SIDDHARTHA NAG Of S. Majumdar & Co. (Applicant's agent)

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in-pct-2001-00239-mum-abstract(30-12-2004).doc

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