RU2240391C2 - Method for processing of textile articles - Google Patents

Abstract

FIELD: textile industry, in particular, processing of textile articles by washing or whitening.

SUBSTANCE: method involves processing of textile article by providing contacting thereof with organic substance forming complex with transition metal, said complex catalyzing textile article whitening process by atmospheric oxygen after processing thereof with given complex and drying. Organic substance may be used in dry state or in the form of solution, such as aqueous liquid for spraying processing of textile fabrics, or washing solution or aerosol liquid used for spraying. Organic substance may contact with dry textile article, with catalysis of whitening of dry textile article with atmospheric oxygen occurring immediately on textile article.

EFFECT: simplified method and increased cleaning effect.

54 cl, 2 tbl, 18 ex

Description

The present invention relates to a method for treating textiles such as washable fabrics, and more particularly, to a method in which atmospheric oxygen bleaching is catalyzed after treatment. The invention also relates to textiles processed in this way.

In a known bleaching treatment, a substrate such as a washable fabric or other textile product is exposed to hydrogen peroxide or substances that can form hydroperoxyl radicals, such as inorganic or organic peroxides.

A preferred approach to the formation of hydroperoxyl whitening radicals involves the use of inorganic peroxides combined with organic precursor compounds. These systems are used for many industrial laundry detergents. For example, various European systems rely on the use of tetraacetylethylenediamine (TAED) as an organic precursor combined with sodium perborate or percarbonate, while in the United States, laundry detergents are usually based on sodium nonanoyloxybenzenesulfonate (SNOBS) as an organic precursor connected to perborate sodium. Alternatively or additionally, hydrogen peroxide and peroxy systems can be activated by bleaching catalysts, for example, iron and ligand complexes N4Py (i.e., N, N-bis (pyridin-2-ylmethyl) -bis (pyridin-2-ylmethylamine) described in WO 95/34628, or the Tran ligand (ie, N, N, N ′, N′-tetra (pyridin-2-ylmethyl) ethylenediamine) described in WO 97/48787. For a long period of time, the possibility of using atmospheric oxygen (air) as a source for bleach, as this eliminates the need for hydroperoxyl-forming systems. Unfortunately, air as such is kinetically inert with respect to bleaching substrates and does not show bleaching activity. Some progress has recently been made in this area. For example, WO 97/38074 describes the use of air to oxidize stains on tissues as a result of air sparging. through an aqueous solution containing an aldehyde and a radical initiator, while in accordance with WO 95/34628 and WO 97/48787 mentioned above, molecular oxygen can be used as an oxide an iron catalyst catalyst as an alternative to a peroxide forming system.

However, known methods describe a whitening action only as long as the substrate is subjected to a bleaching treatment. Thus, one cannot expect that hydrogen peroxide or peroxide bleaching systems will continue to have a bleaching effect on the substrate to be treated, such as the fabric to be washed after washing and drying, since it is assumed that the bleaches themselves or any activators necessary for the bleaching systems are removed from substrate, spend or deactivate at the end of the washing and drying cycle.

It is desirable to be able to process the textile product in such a way that after the end of processing, a bleaching effect can be observed on it. Moreover, it would be desirable to be able to bleach textiles, such as washable fabrics, so that residual bleaching occurs after the fabric has been processed and dried.

We found that this goal can be achieved by applying the method in accordance with this invention by catalysis of bleaching the substrate with atmospheric oxygen after processing the substrate.

Accordingly, the present invention provides a method for treating a textile product by contacting it with an organic substance that forms a complex with a transition metal, this complex catalyzing the bleaching of a textile product with atmospheric oxygen after processing.

The present invention also contemplates the use or deposition on a dry textile product of the aforementioned organic substance, wherein atmospheric oxygen bleaching is catalyzed on the textile product.

Obtaining a bleaching effect even after processing a textile product is advantageous in that the positive effect of bleaching can be extended. Moreover, since the bleaching effect is manifested on the textile product after processing, the processing itself, such as a laundry washing cycle, for example, can be shortened.

Moreover, since the whitening effect is achieved using atmospheric oxygen after processing the textile product, hydrogen peroxide or peroxide-based whitening systems can be removed from the processing substance.

Organic matter can be used to influence a textile product in any suitable way. For example, it can be used in a dry form, such as a powder, in the form of a liquid subsequently dried, for example, in the form of an aqueous sprayed liquid for treating fabrics, a washing liquid for cleaning clothes, an anhydrous liquid for dry cleaning or a spray of aerosol liquid. As described below, other suitable means of exposing the textile to an organic substance may be used.

Any suitable textile product that is susceptible to bleaching, or that product that is desirable to be bleached, can be used. Textiles preferably include fabric-sewed linen or clothing.

The method of the invention is preferably applied to the fabric to be washed using an aqueous treatment solution. In particular, the processing can be carried out in a washing cycle for cleaning clothes. More preferably, the treatment is carried out in an aqueous bleaching liquid for washing.

In a preferred embodiment, the treated textile is dried at ambient temperature or at elevated temperature.

Bleaching also occurs when the substrate is simply left in contact with organic matter for a sufficiently long period of time. However, it is preferred that the organic substance is in an aqueous medium and that the aqueous medium on or containing the substrate is mixed.

Organic matter can be used to expose the textile fiber in any suitable manner. For example, it can be used in a dry form, such as a powder, in the form of a liquid subsequently dried, for example in the form of an aqueous sprayed liquid for treating fabrics, washing liquid for cleaning clothes, anhydrous liquid for dry cleaning or sprayed aerosol liquid.

In a preferred embodiment, the treated textile is dried at ambient temperature or elevated temperature.

In a particularly preferred embodiment, the method of the invention is applied to the fabric to be washed using an aqueous treatment solution. In particular, the treatment may be carried out during or in addition to the substantially known washing cycle when cleaning the laundry. More preferably, the treatment is carried out in an aqueous washing liquid. Organic matter can enter the washing liquid in the form of powder, granules, balls, tablets, bars, strips or other similar solid forms. The solid form may include a carrier, which may be crushed, in the form of a sheet or have a three-dimensional shape. The carrier may be dispersed or dissolved in the washing liquid or remain substantially intact. In accordance with other options, the organic substance can enter the washing liquid in the form of a paste, gel or liquid concentrate.

A particular advantage is that the organic substance used in the method in accordance with this invention uses atmospheric oxygen for bleaching. This eliminates the need for peroxide bleaches and / or other relatively large quantities of reactive substances during processing. Therefore, it is necessary to use only a relatively small amount of active whitening substance, which opens up new possibilities for its introduction, which could not be used previously. Thus, although it is preferable to include organic matter in a composition typically used in a washing process, such as pre-treatment, main wash, conditioning or ironing compositions, other means that ensure the presence of organic matter in the washing liquid can also be used. .

For example, it is contemplated that the organic substance may be in the form of a mass from which it is slowly released during a full or partial washing process. Such a release may occur during one or more washes. In the latter case, it is contemplated that the organic matter may be released from the carrier substrate used during the washing process, for example from a mass placed in the dispersing device of the washing machine, elsewhere in the feed system or into the drum of the washing machine. When placed in the drum of the washing machine, the carrier can move freely or be attached relative to the drum. Such attachment can be carried out by mechanical means, for example, teeth located on the wall of the drum, or using other forces, for example magnetic. Modification of the washing machine, equipped with a device for holding such a carrier, provides for such devices, known from a similar use of toilet bars. Freely moving carriers, such as closures for dispensing surfactants and / or other detergent ingredients into the wash, may include a device for releasing organic matter into the wash.

Alternatively, the organic substance may be introduced as a preferably soluble washing additive. The additive may have any physical form used for washing additives, including powders, granules, balls, sheets, tablets, bars, strips and other solid forms, or in the form of a paste, gel or liquid. The dosage of the additive may be single or in an amount determined by the user. Despite the intended use of such additives in the main washing cycle, their use in conditioning or drying cycles is not ruled out.

This invention is not limited by the circumstances of the use of the washing machine and can be used when washing in any other container. In these circumstances, it is contemplated that the organic substance may be introduced by slowly adding from a bowl, bucket, or other applicable container or accessory such as a brush, washcloth, stirrer, or other suitable means.

Suitable pretreatment agents for applying the organic material to the textile material before the main wash include spray guns, pens, ball devices, strips, semi-solid rods and soaked wipes or wipes containing microcapsules. Such agents are well known in the similar field of application of deodorants and / or stain removal from textiles. Such agents are used in cases where the organic substance is applied after the main washing and / or conditioning steps, i.e. before or after ironing or drying the fabric. For example, an organic substance can be applied using tapes, sheets or adhesive patches with an organic substance applied to them or impregnated with them or containing microcapsules. Organic matter, for example, can be introduced into the dryer sheet so as to be activated or released during drying in the drum, or the substance can be contained in an impregnated or microcapsule-containing sheet so that it can be applied to the textile product when ironed.

Organic matter may include a preformed ligand-transition metal complex. Alternatively, the organic material may include a free ligand complexed with a transition metal already present in water, or complexed with a transition metal present in the substrate. Organic matter can also be included as a composition of a free ligand or a metal-ligand complex replaced by a transition metal and a transition metal source, wherein the complex is formed in an in situ environment.

Organic matter forms a complex with one or more transition metals, in the latter case such as, for example, a binuclear complex. Suitable transition metals, for example, include oxidized state manganese II-V, iron I-IV, copper I-III, cobalt I-III, nickel I-III, chromium II-VII, silver I-II, titanium II-IV, tungsten IV-VI, palladium II, ruthenium II-V, vanadium II-V and molybdenum II-VI.

In a preferred embodiment of the invention, the organic substance forms a complex of the general formula (A1)

[M _a L _k X _n ] Y _m

where M is a metal selected from Mn (II) - (III) - (IV) - (V), Cu (I) - (II) - (III), Fe (I) - (II) - (III) - (IV), Co (I) - (II) - (III), Ni (I) - (II) - (III), Cr (II) - (III) - (IV) - (V) - (VI) - (VII), Ti (II) - (III) - (IV), V (II) - (III) - (IV) - (V), Mo (II) - (III) - (IV) - (V ) - (VI), W (IV) - (V) - (VI), Pd (II), Ru (II) - (III) - (IV) - (V) and Ag (I) - (II)) preferably selected from Mn (II) - (III) - (IV) - (V), Cu (I) - (II) - (III), Fe (I) - (II) - (III) - (IV) and Co (I) - (II) - (III);

L is the ligand described here or its analogue with an attached or removed proton;

X is a coordinating group selected from any mono-, bi- or tri-charged anions and any neutral molecules capable of coordinating the metal in a mono-, bi- or tridental manner, preferably selected from O ^2- , RBO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{2}}$ , RCOO ^- , RCONR ^- , OH ^- , NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{2}}$ , NO, CO, S ^2- , RS ^- , РО $\genfrac{}{}{0ex}{}{\text{4-}}{\text{3}}$ derivatives of sodium tripolyphosphate (STP) anions, PO ₃ OR ^3- , H ₂ O, СО $\genfrac{}{}{0ex}{}{\text{2-}}{\text{3}}$ NSO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , ROH, NRR'R '', RCN, Cl ^- , Br ^- , OCN ^- , SCN ^- , CN ^- , N $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , F ^- , I ^- , RO ^- , ClO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ SO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{4}}$ HSO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , SO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{3}}$ and RSO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ more preferably selected from O ^2- , RBO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{2}}$ , RCOO ^- , OH ^- , NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{2}}$ , NO, CO, CN ^- , S ^2- , RS ^- , РО $\genfrac{}{}{0ex}{}{\text{4-}}{\text{3}}$ , H ₂ O, WITH $\genfrac{}{}{0ex}{}{\text{2-}}{\text{3}}$ NSO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , ROH, NRR'R '', Cl ^- , Br ^- , OCN ^- , SCN ^- , RCN, N $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , F ^- , I ^- , RO ^- , ClO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ SO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{4}}$ HSO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , SO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{3}}$ and PSO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ (preferably CF ₃ SO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ );

Y is any uncoordinated counterion, preferably selected from ClO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , BR $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , [FeCl ₄ ] ^- , PF $\genfrac{}{}{0ex}{}{\text{-}}{\text{6}}$ , RCOO ^- , NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{2}}$ , RO ^- , N ⁺ RR'R``R ''', Cl <sup>-</sup> , Br <sup>-</sup> , F <sup>-</sup> , I <sup>-</sup> , PSO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , S <sub>2</sub> O $\genfrac{}{}{0ex}{}{\text{2-}}{\text{6}}$ , OCN <sup>-</sup> , SCN <sup>-</sup> , Li <sup>+</sup> , Ba <sup>2+</sup> , Na <sup>+</sup> , Mg <sup>2+</sup> , K <sup>+</sup> , Ca <sup>2+</sup> , Cs <sup>+</sup> , PR $\genfrac{}{}{0ex}{}{\text{+}}{\text{4}}$ RBO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{2}}$ SO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{4}}$ HSO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , SO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{3}}$ SbCl $\genfrac{}{}{0ex}{}{\text{-}}{\text{6}}$ CuCl $\genfrac{}{}{0ex}{}{\text{2-}}{\text{4}}$ , CN, PO $\genfrac{}{}{0ex}{}{\text{3-}}{\text{4}}$ HPO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{4}}$ , H <sub>2</sub> PO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ derived from STP anions, CO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{3}}$ NSO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ and bf $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ more preferably selected from ClO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , BR $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , [FeCl <sub>4</sub> ] <sup>-</sup> , PF $\genfrac{}{}{0ex}{}{\text{-}}{\text{6}}$ , RCOO <sup>-</sup> , NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{2}}$ , RO <sup>-</sup> , N <sup>+</sup> RR'R``R ''', Cl ^- , Br ^- , F ^- , I ^- , RSO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ (preferably CF ₃ SO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ ), S ₂ O $\genfrac{}{}{0ex}{}{\text{2-}}{\text{6}}$ , OCN ^- , SCN ^- , Li ⁺ , Ba ²⁺ , Na ⁺ , Mg ²⁺ , PR $\genfrac{}{}{0ex}{}{\text{+}}{\text{4}}$ , K ⁺ , Ca ²⁺ , SO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{4}}$ HSO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , SO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{3}}$ and bf $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ ;

R, R ′, R ″, R ″ ″ independently represent a group selected from hydrogen, hydroxyl, —OR (where R is alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or carbonyl derivative group), —OAr, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and carbonyl derivatives, each of R, Ar, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and carbonyl derivatives is optionally substituted with one or more functional groups E or R6 together with R7 and independently, R8 together with R9 are oxygen, where E selected from functional groups containing oxygen, sulfur, phosphorus, nitrogen, selenium, halogens, as well as any electron-giving and / or removing groups, preferably R, R ′, R ″, R ″ ″ are hydrogen, optionally substituted by alkyl or aryl, more preferably hydrogen or optionally substituted phenyl, naphthyl or C _1-4 alkyl;

a is an integer from 1 to 10, preferably from 1 to 4;

k is an integer from 1 to 10;

n = 0 or an integer from 1 to 10, preferably from 1 to 4;

m = 0 or an integer from 1 to 20, preferably from 1 to 8.

Ligand L preferably has the general formula (BI)

where g = 0 or an integer from 1 to 6;

r is an integer from 1 to 6;

s = 0 or an integer from 1 to 6;

Z1 and Z2 independently represent a heteroatom or a heterocyclic or heteroaromatic ring, wherein Z1 and / or Z2 are optionally substituted with one or more functional groups E described below;

Q1 and Q2 independently represent a group of the formula

where 10> d + e + f> 1; d is 0-9; e = 0-9; f is 0-9;

each Y1 is independently selected from -O-, -S-, -SO-, -SO ₂ -, - (G ¹ ) N-, - (G ¹ ) (G ^-2 ) N- (where G ¹ and G ² have the following meanings), —C (O) -, arylene, alkylene, heteroarylene, —P— and —P (O) -;

if s> 1, then each - [- Z1 (R1) - (Q1) _r -] - group is determined independently from each other;

R1, R2, R6, R7, R8, R9 independently represent a group selected from hydrogen, hydroxyl - OR (where R is alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or carbonyl derivative group), -OAr, alkyl , alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and carbonyl derivatives, each of R, Ar, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and carbonyl derivatives is optionally substituted with one or more functional groups E, or R6 together with R7 and independently R8 together with R9 Representing is oxygen;

E is selected from functional groups containing oxygen, sulfur, phosphorus, nitrogen, selenium, halogens, as well as any electron-giving and / or removing groups (preferably E is selected from hydroxy, mono- or polycarboxylate derivatives, aryl, heteroaryl, sulfonate, thiol ( -RSH), thioethers (-RS-R '), disulfides (-RSSR'), dithiolenes, mono- or polyphosphates, electron-giving groups and electron-removing groups, as well as groups of formulas (G ¹ ) (G ² ) N-, ( G ¹ ) (G ² ) (G ³ ) N-, (G ¹ ) (G ² ) NC (O) -, G ³ O- and G ³ C (O) -, where each of G ¹ , G ² and G ³ are independently selected from hydrogen, alkyl, RE notdayuschih and elektronudalyayuschih groups (in addition to the foregoing));

or one of R1-R9 represents a bridging group linked to another residue having the same general formula;

T1 and T2 independently of each other are groups R4 and R5, where R4 and R5 have the meanings given for R1-R9, and if g = 0, as> 0, then R1 together with R4 and / or R2 together with R5 can optionally independently = CH-R10, where R10 is as defined for R1-9, or

T1 and T2 together (-T2-T1-) can be a covalent bond when s> 1 and g> 0;

if Z1 and / or Z2 are N, T1 and T2 together are a single bond, and R1 and / or R2 are absent, then Q1 and / or Q2 independently of each other can be a group of the formula = CH - [- Y1-] _e -CH =;

optionally any two or more of R1, R2, R6, R7, R8, R9 are independently linked together by a covalent bond;

if Z1 and / or Z2 are O, then R1 and / or R2 do not exist;

if Z1 and / or Z2 are S, N, P, B or Si, then R1 and / or R2 may be absent;

if Z1 and / or Z2 are a heteroatom substituted by a functional group E, then R1 and / or R2 and / or R4 and / or R5 may be absent.

The Z1 and Z2 groups are preferably independently from each other an optionally substituted heteroatom selected from N, P, O, S, B and Si, or an optionally substituted heterocyclic ring, or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidines, pyrazine, pyramidine , pyrazole, pyrrole, imidazole, benzimidazole, quinolein, isoquinoline, carbazole, indole, isoindole, furan, thiophene, oxazole and thiazole.

The R1-R9 groups are preferably independently selected from —H, hydroxy-C ₀ -C ₂₀ -alkyl, halo-C ₀ -C ₂₀ -alkyl, nitroso, formyl-C ₀ -C ₂₀ -alkyl, carboxyl-C ₀ -C ₂₀ alkyl, their esters and salts, carbamoyl-C ₀ -C ₂₀ -alkyl, sulfo-C ₀ -C ₂₀ -alkyl, their esters and salts, sulfamoyl-C ₀ -C ₂₀ -alkyl, amino C ₀ -C ₂₀ alkyl, aryl-C ₀ -C ₂₀ -alkyl, heteroaryl-C ₀ -C ₂₀ -alkyl, C ₀ -C ₂₀ -alkyl, alkoxy-C ₀ -C ₈ -alkyl, carbonyl-C ₀ -C ₆ alkoxy, aryl-C ₀ -C ₆ -alkyl and C ₀ -C ₂₀ -alkylamide.

One of R1-R9 may be a bridging group linking the ligand residue to a second ligand residue, preferably having the same general structure. In this case, the bridging group may have the formula

-C _{n '} (R11) (R12) - (D) _p -C _m' (R11) (R12) -

bonded between two residues, where p = 0 or 1, D is selected from a heteroatom or heteroatom-containing group, or D 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, provided that n ′ + m ′ <= 4, R11 and R12 each independently of one another are preferably selected from —H, NR13 and OR14, alkyl, aryl optionally substituted, and R13 and R14 each independently optionally substituted, selected from —H, alkyl, aryl. Alternatively or additionally, two or more of R1-R9 together represent a bridging group bonding atoms, preferably heteroatoms, in the same residue, wherein the bridging group is preferably an alkylene, oxyalkylene or heteroaryl-containing bridge.

In the first embodiment, in accordance with formula (BI), the groups T1 and T2 together form a simple bond, and s> 1 in accordance with the general formula (BII)

where Z3 independently represents a group indicated for Z1 or Z2; R3 independently represents a group indicated for R1-R9; Q3 independently represents a group indicated for Q1, Q2; h = 0 or an integer from 1 to 6; and s ’= s-1.

In a first specific embodiment of the first embodiment, in the general formula (BII) s ’= 1, 2 or 3; r = g = h = 1; d is 2 or 3; e = f = 0; R6 = R7 = H, and the ligand preferably has the general formula selected from

and more preferably, selected from

In these preferred examples, R1, R2, R3 and R4 are preferably independently selected from —H, alkyl, aryl, heteroaryl, and / or one of R1-R4 is a bridging group bonded to another residue having the same general formula and / or two or more of R1-R4 together represent a bridging group linking the N atoms in the same residue, wherein the bridging group is an alkylene, oxyalkylene or heteroaryl-containing bridge, preferably heteroarylene. More preferably, R1, R2, R3 and R4 are independently selected from —H, methyl, ethyl, isopropyl, a nitrogen-containing heteroaryl, or a bridging group bonded to another moiety having the same general formula or linking N atoms in the same moiety wherein the bridging group is alkylene or hydroxyalkylene.

In accordance with this first option in the complex [M _a L _k X _n ] Y _m preferably

M = Mn (II) - (IV), Cu (I) - (III), Fe (II) - (III), Co (II) - (III);

X = CH ₃ CN, OH ₂ , Cl ^- , Br ^- , OCN ^- , N $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , SCN ^- , OH ^- , O ^2- , PO $\genfrac{}{}{0ex}{}{\text{3-}}{\text{4}}$ , C ₆ H ₅ BO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{2}}$ , RCOO ^- ;

Y = ClO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ BPh $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , Br ^- , Cl ^- , [FeCl ₄ ] ^- , PF $\genfrac{}{}{0ex}{}{\text{-}}{\text{6}}$ NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ ;

a = 1, 2, 3, 4;

n is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9;

m = 1, 2, 3, 4 and

k = 1, 2, 4.

In a second specific embodiment of the first embodiment, in the general formula (BII) s ’= 2; r = g = h = 1; d = f = 0; e = 1, and each of Y1 is independently alkylene or heteroarylene. The ligand preferably has the general formula

where A ₁ , A ₂ , A ₃ , A _{4 are} independently selected from C _1-9 alkylene or heteroarylen groups and

N ₁ and N ₂ independently from each other represent a heteroatom or heteroarylene group.

In a preferred second embodiment of the first embodiment, N ₁ is aliphatic nitrogen, N ₂ is a heteroarylene group, R1, R2, R3, R4 are independently —H, alkyl, aryl or heteroaryl, and A ₁ , A ₂ , A ₃ , A ₄ each independently represents —CH ₂ -.

One of R1-R4 may be a bridging group linked to another residue having the same general formula, and / or two or more of R1-R4 together may be a bridging group linking N atoms in the same residue, with this bridging group is an alkylene, oxyalkylene or heteroaryl-containing bridge. Preferably, R1, R2, R3 and R4 are independently selected from —H, methyl, ethyl, isopropyl, a nitrogen-containing heteroaryl or a bridging group bonded to another residue having the same general formula or linking N atoms in the same residue, wherein the bridging group is alkylene or oxyalkylene. Particularly preferably, the ligand has the General formula

where each of R1 and R2 independently of one another is —H, alkyl, aryl or heteroaryl.

According to this second embodiment of the first embodiment, the complex [M _a L _k X _n ] Y _{m is} preferably

M = Fe (II) - (III), Mn (II) - (IV), Cu (II), Co (II) - (III);

X = CH ₃ CN, OH ₂ , Cl ^- , Br ^- , OCN ^- , N $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , SCN ^- , OH ^- , O ^2- , PO $\genfrac{}{}{0ex}{}{\text{3-}}{\text{4}}$ , C ₆ H ₅ BO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{2}}$ , RCOO ^- ;

Y = ClO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ BPh $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , Br ^- , Cl ^- , [FeCl ₄ ] ^- , PF $\genfrac{}{}{0ex}{}{\text{-}}{\text{6}}$ NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ ;

a = 1, 2, 3, 4;

n is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9;

m = 1, 2, 3, 4 and

k = 1, 2, 4.

In a third specific embodiment of the first embodiment, in the general formula (BII) s ’= 2, a r = g = h = 1 in accordance with the general formula

In this third embodiment of the first embodiment, each of Z1-Z4 is preferably a heteroaromatic ring; e = f = 0; d is 1; a R7 is absent, while preferably R1 = R2 = R3 = R4 = 2,4,6-trimethyl-3-SO ₃ Na-phenyl, 2,6-di-Cl-3 (or 4) -SO ₃ Na-phenyl .

Alternatively, each of Z1-Z4 is N;

R1-R4 are absent; both Q1 and Q3 are = CH - [- Y1-] _e -CH, and both Q2 and Q4 are —CH ₂ - [- Y1-] _n —CH ₂ -.

Thus, preferably the ligand has the general formula

where A represents an optionally substituted alkylene, optionally interrupted by a heteroatom, and n = 0 or an integer from 1 to 5.

Preferably, R1-R6 are hydrogen, n = 1, and A = —CH ₂ -, —CHOH—, —CH ₂ N (R) CH ₂ - or —CH ₂ CH ₂ N (R) CH ₂ CH ₂ -, where R represents hydrogen or alkyl, more preferably A = —CH ₂ , —CHOH— or —CH ₂ CH ₂ N (R) CH ₂ CH ₂ -.

According to this third embodiment of the first embodiment, the complex [M _a L _k X _n ] Y _{m is} preferably

M = Mn (II) - (IV), Co (II) - (III), Fe (II) - (III);

X = CH ₃ CN, OH ₂ , Cl ^- , Br ^- , OCN ^- , N $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , SCN ^- , OH ^- , O ^2- , PO $\genfrac{}{}{0ex}{}{\text{3-}}{\text{4}}$ , C ₆ H ₅ BO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{2}}$ , RCOO ^- ;

Y = ClO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ BPh $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , Br ^- , Cl ^- , [FeCl ₄ ] ^- , PF $\genfrac{}{}{0ex}{}{\text{-}}{\text{6}}$ NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ ;

a = 1, 2, 3, 4;

n is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9;

m = 1, 2, 3, 4 and

k = 1, 2, 4.

In the second embodiment, in accordance with formula (B1), T1 and T2 independently of one another are groups R4, R5 having the meanings indicated for R1-R9, in accordance with general formula (BIII)

In a first specific embodiment of the second embodiment, in the general formula (BIII) s = 1; r is 1; g is 0; d = f = 1; e is 1-4; Y1 = —CH ₂ -; and R1 together with R4 and / or R2 together with R5 independently of each other are = CH-R10, where R10 has the meanings indicated for R1-R9. In one example, R2 together with R5 represents = CH-R10, wherein R1 and R4 are two separate groups. Alternatively, both R1 together with R4, and R2 together with R5 may independently be = CH-R10. Thus, preferred ligands, for example, may have the formula

The ligand is preferably selected from

where R1 and R2 are selected from optionally substituted phenols, heteroaryl-C ₀ -C ₂₀ -alkyls, R3 and R4 are selected from -H, alkyl, aryl, optionally substituted phenols, heteroaryl-C ₀ -C ₂₀ -alkyl, alkylaryl, aminoalkyl, alkoxy, wherein R1 and R2 are more preferably selected from optionally substituted phenols, heteroaryl-C ₀ -C ₂ -alkyls, R3 and R4 are selected from -H, alkyl, aryl, optionally substituted phenols, nitrogen-heteroaryl-C ₀ -C ₂₀ -alkyls.

In accordance with this first specific implementation of the second option in the complex [M _a L _k X _n ] Y _m preferably

M = Mn (II) - (IV), Co (II) - (III), Fe (II) - (III);

X = CH ₃ CN, OH ₂ , Cl ^- , Br ^- , OCN ^- , N $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , SCN ^- , OH ^- , O ^2- , PO $\genfrac{}{}{0ex}{}{\text{3-}}{\text{4}}$ , C ₆ H ₅ BO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{2}}$ , RCOO ^- ;

Y = ClO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ BPh $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , Br ^- , Cl ^- , [FeCl ₄ ] ^- , PF $\genfrac{}{}{0ex}{}{\text{-}}{\text{6}}$ NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ ;

a = 1, 2, 3, 4;

n is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9;

m = 1, 2, 3, 4 and

k = 1, 2, 4.

In a second specific embodiment of the second embodiment, in the general formula (BIII) s = 1; r is 1; g is 0; d = f = 1; e is l-4; Y1 = -C (R ’) (R’ ’), where R’ and R ’’ independently have the meanings indicated for R1-R9. The ligand preferably has the general formula

The groups R1, R2, R3, R4, R5 in this formula are preferably —H or C ₀ —C ₂₀ alkyl, n = 0 or 1, R6 is —H, alkyl, —OH or —SH, and R7, R8, R9, R10 are each preferably independently selected from —H, C ₀ -C ₂₀ -alkyl, heteroaryl-C ₀ -C ₂₀ -alkyl, alkoxy-C ₀ -C ₈ -alkyl and amino-C ₀ -C ₂₀ -alkyl.

In accordance with this second specific embodiment of the second embodiment, the complex [M _a L _k X _n ] Y _{m is} preferably

M = Mn (II) - (IV), Fe (II) - (III), Cu (II), Co (II) - (III);

X = CH ₃ CN, OH ₂ , Cl ^- , Br ^- , OCN ^- , N $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , SCN ^- , OH ^- , O ^2- , PO $\genfrac{}{}{0ex}{}{\text{3-}}{\text{4}}$ , C ₆ H ₅ BO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{2}}$ , RCOO ^- ;

Y = ClO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ BPh $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , Br ^- , Cl ^- , [FeCl ₄ ] ^- , PF $\genfrac{}{}{0ex}{}{\text{-}}{\text{6}}$ NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ ;

a = 1, 2, 3, 4;

n is 0, 1, 2, 3, 4;

m = 1, 2, 3, 4, 5, 6, 7, 8 and

k = 1, 2, 3, 4.

In a third specific embodiment of the second embodiment, in the general formula (BIII) s = 0; g is 1; d = e = 0; f = 1-4. The ligand preferably has the general formula

More preferably, the ligand has the general formula

where R1, R2, R3 have the meanings indicated for R2, R4, R5.

According to this third specific embodiment of the second embodiment, the complex [M _a L _k X _n ] Y ^{m is} preferably

M = Mn (II) - (IV), Fe (II) - (III), Cu (II), Co (II) - (III);

X = CH ₃ CN, OH ₂ , Cl ^- , Br ^- , OCN ^- , N $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , SCN ^- , OH ^- , O ^2- , PO $\genfrac{}{}{0ex}{}{\text{3-}}{\text{4}}$ , C ₆ H ₅ BO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{2}}$ , RCOO ^- ;

Y = ClO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ BPh $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , Br ^- , Cl ^- , [FeCl ₄ ] ^- , PF $\genfrac{}{}{0ex}{}{\text{-}}{\text{6}}$ NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ ;

a = 1, 2, 3, 4;

n is 0, 1, 2, 3, 4;

m = 1, 2, 3, 4, 5, 6, 7, 8 and

k = 1, 2, 3, 4.

In a fourth specific embodiment of the second embodiment, the organic substance forms a complex of the general formula (A)

[LMX _n ] ^z Y _q

in which M is iron in the oxidation state of II, III, IV or V, manganese in the oxidation state of II, III, IV, VI or VII, copper in the oxidation state of I, II or III, cobalt in the oxidation state of II, III or IV either chromium in oxidation state II-VI;

X represents a coordinating group;

n = 0 or an integer from 0 to 3;

z represents the charge of the complex and is equal to a positive integer, zero or a negative number;

Y is a counterion, the form of which depends on the charge of the complex;

q = z / [charge Y] and

L is a five-tooth ligand of the general formula (B)

where each of R ¹ and R ² independently from each other represents-R ⁴ -R ⁵ ,

R ³ represents hydrogen, optionally substituted by alkyl, aryl or arylalkyl, or —R ⁴ —R ⁵ ,

each of R ⁴ independently of one another is a single bond or an optionally substituted alkylene, alkenylene, hydroxyalkylene, aminoalkylene, alkylene ether, carboxylic acid ester or carboxylic amide and

each of R ⁵ independently from each other 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.

Ligand L having the above general formula (B) is a pentadentate ligand. The term "pentadental" in this description means that five heteroatoms can be coordinated with the metal ion M in the metal complex.

In formula (B), one coordinating heteroatom is a nitrogen atom in the main chain of methylamine and one coordinating heteroatom is preferably contained in each of the four R ¹ and R ² side groups. All coordinating heteroatoms are preferably nitrogen atoms.

Ligand L of the formula (B) preferably includes at least two substituted or unsubstituted heteroaryl groups in four side groups. The heteroaryl group is preferably a pyridin-2-yl group, and being substituted, preferably a methyl or ethyl substituted pyridin-2-yl group. More preferably, the heteroaryl group is an unsubstituted pyridin-2-yl group. Preferably, the heteroaryl group is bonded to methylamine and preferably to its R atom via a methylene group. Ligand L of the formula (B) preferably contains at least one optionally substituted aminoalkyl side group, more preferably two aminoethyl side groups, in particular 2- (N-alkyl) aminoethyl or 2- (N, N-dialkyl) aminoethyl.

Thus, in formula (B), R ^{1 is} preferably pyridin-2-yl or R ² is pyridin-2-ylmethyl. R ¹ or R ^{2 is} preferably 2-aminoethyl, 2- (N-methyl (ethyl)) aminoethyl or 2- (N, N-dimethyl (ethyl)) aminoethyl. When substituted, R ^{5 is} preferably 3-methylpyridin-2-yl. R ^{3 is} preferably hydrogen, benzyl or methyl.

Examples of preferred L ligands of formula (B) in their simplest form include

(i) pyridin-2-yl-containing ligands, such as

N, N-bis (pyridin-2-ylmethyl) bis (pyridin-2-yl) methylamine;

N, N-bis (pyrazol-1-ylmethyl) bis (pyridin-2-yl) methylamine;

N, N-bis (imidazol-2-ylmethyl) bis (pyridin-2-yl) methylamine;

N, N-bis (1,2,4-triazol-1-ylmethyl) bis (pyridin-2-yl) methylamine;

N, N-bis (pyridin-2-ylmethyl) bis (pyrazol-1-yl) methylamine;

N, N-bis (pyridin-2-ylmethyl) bis (imidazol-2-yl) methylamine;

N, N-bis (pyridin-2-ylmethyl) bis (1,2,4-triazol-1-yl) methylamine;

N, N-bis (pyridin-2-ylmethyl) -1,1-bis (pyridin-2-yl) -1-aminoethane;

N, N-bis (pyridin-2-ylmethyl) -1,1-bis (pyridin-2-yl) -2-phenyl-1-aminoethane;

N, N-bis (pyrazol-1-ylmethyl) -1,1-bis (pyridin-2-yl) -1-aminoethane;

N, N-bis (pyrazol-1-ylmethyl) -1,1-bis (pyridin-2-yl) -2-phenyl-1-aminoethane;

N, N-bis (imidazol-2-ylmethyl) -1,1-bis (pyridin-2-yl) -1-aminoethane;

N, N-bis (imidazol-2-ylmethyl) -1,1-bis (pyridin-2-yl) -2-phenyl-1-aminoethane;

N, N-bis (1,2,4-triazol-1-ylmethyl) -1,1-bis (pyridin-2-yl) -1-aminoethane;

N, N-bis (1,2,4-triazol-1-ylmethyl) -1,1-bis (pyridin-2-yl) -2-phenyl-1-aminoethane;

N, N-bis (pyridin-2-ylmethyl) -1,1-bis (pyrazol-1-yl) -1-aminoethane;

N, N-bis (pyridin-2-ylmethyl) -1,1-bis (pyrazol-1-yl) -2-phenyl-1-aminoethane;

N, N-bis (pyridin-2-ylmethyl) -1,1-bis (imidazol-2-yl) -1-aminoethane;

N, N-bis (pyridin-2-ylmethyl) -1,1-bis (imidazol-2-yl) -2-phenyl-1-aminoethane;

N, N-bis (pyridin-2-ylmethyl) -1,1-bis (1,2,4-triazol-1-yl) -1-aminoethane;

N, N-bis (pyridin-2-ylmethyl) -1,1-bis (1,2,4-triazol-1-yl) -1-aminoethane;

N, N-bis (pyridin-2-ylmethyl) -1,1-bis (pyridin-2-yl) -1-aminoethane;

N, N-bis (pyridin-2-ylmethyl) -1,1-bis (pyridin-2-yl) -1-aminohexane;

N, N-bis (pyridin-2-ylmethyl) -1,1-bis (pyridin-2-yl) -2-phenyl-1-aminoethane;

N, N-bis (pyridin-2-ylmethyl) -1,1-bis (pyridin-2-yl) -2- (4-sulfonic acid-phenyl) -1-aminoethane;

N, N-bis (pyridin-2-ylmethyl) -1,1-bis (pyridin-2-yl) -2- (pyridin-2-yl) -1-aminoethane;

N, N-bis (pyridin-2-ylmethyl) -1,1-bis (pyridin-2-yl) -2- (pyridin-3-yl) -1-aminoethane;

N, N-bis (pyridin-2-ylmethyl) -1,1-bis (pyridin-2-yl) -2- (pyridin-4-yl) -1-aminoethane;

N, N-bis (pyridin-2-ylmethyl) -1,1-bis (pyridin-2-yl) -2- (1-alkylpyridinium-4-yl) -1-aminoethane;

N, N-bis (pyridin-2-ylmethyl) -1,1-bis (pyridin-2-yl) -2- (1-alkylpyridinium-3-yl) -1-aminoethane;

N, N-bis (pyridin-2-ylmethyl) -1,1-bis (pyridin-2-yl) -2- (1-alkylpyridinium-2-yl) -1-aminoethane;

(ii) 2-aminoethyl-containing ligands, such as

N, N-bis (2- (N-alkyl) aminoethyl) bis (pyridin-2-yl) methylamine;

N, N-bis (2- (N-alkyl) aminoethyl) bis (pyrazol-1-yl) methylamine;

N, N-bis (2- (N-alkyl) aminoethyl) bis (imidazol-2-yl) methylamine;

N, N-bis (2- (N-alkyl) aminoethyl) bis (1,2,4-triazol-1-yl) methylamine;

N, N-bis (2- (N, N-dialkyl) aminoethyl) bis (pyridin-2-yl) methylamine;

N, N-bis (2- (N, N-dialkyl) aminoethyl) bis (pyrazol-1-yl) methylamine;

N, N-bis (2- (N, N-dialkyl) aminoethyl) bis (imidazol-2-yl) methylamine;

N, N-bis (2- (N, N-dialkyl) aminoethyl) bis (1,2,4-triazol-1-yl) methylamine;

N, N-bis (pyridin-2-ylmethyl) bis (2-aminoethyl) methylamine;

N, N-bis (pyrazol-1-ylmethyl) bis (2-aminoethyl) methylamine;

N, N-bis (imidazol-2-ylmethyl) bis (2-aminoethyl) methylamine;

N, N-bis (1,2,4-triazol-1-ylmethyl) bis (2-aminoethyl) methylamine.

More preferred ligands are

N, N-bis (pyridin-2-ylmethyl) bis (pyridin-2-yl) methylamine, hereinafter referred to as N4Py;

N, N-bis (pyridin-2-ylmethyl) -1,1-bis (pyridin-2-yl) -1-aminoethane, hereinafter referred to as MeN4Py;

N, N-bis (pyridin-2-ylmethyl) -1,1-bis (pyridin-2-yl) -2-phenyl-1-aminoethane, hereinafter referred to as BzN4Py.

In an alternative fourth specific embodiment of the second embodiment, the organic substance forms a complex of general formula (A) including the above ligand (B), however, provided that R ^{3 is} not hydrogen.

In a fifth specific embodiment of the second embodiment, the organic substance forms a complex of the aforementioned general formula (A), where, however, L is a pentadent or hexadentate ligand of general formula (C)

R ¹ R ¹ NW-NR ¹ R ²

where each of R ¹ independently from each other represents -R ³ -V, in which R ³ represents an optionally substituted alkylene, alkenylene, hydroxyalkylene, aminoalkylene or simple alkylene ether, and V represents an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl;

W is an optionally substituted alkylene bridging group selected from —CH ₂ CH ₂ -, —CH ₂ CH ₂ CH ₂ -, —CH ₂ CH ₂ CH ₂ CH ₂ -, —CH ₂ —C ₆ H ₄ —CH ₂ - , —CH ₂ —C ₆ H ₁₀ —CH ₂ - and —CH ₂ —C ₁₀ H ₆ —CH ₂ -, and

R ² represents a group selected from R ¹ , as well as alkyl, aryl and aralkyl groups optionally substituted with a substituent selected from oxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic acid ester, sulfonate, amine, alkylamine and N ⁺ (R ⁴ ) ₃ , wherein R ^{4 is} selected from hydrogen, alkanyl, alkenyl, arylalkanyl, arylalkenyl, hydroxyalkanyl, hydroxyalkenyl, aminoalkanyl, aminoalkenyl, alkanyl and alkenyl ethers.

Ligand L having the above general formula (C) is a five-tooth ligand or, if R ¹ = R ² is a six-tooth ligand. As indicated above, “pentadentate” means that five heteroatoms can be coordinated with the metal ion M in the metal complex. Similarly, “hexadedentate” means that six heteroatoms can in principle be coordinated with metal ion M. However, in this case, it is believed that one of the “arms” in the complex is not connected, so the hexadedentate ligand is five-coordinating.

In formula (C), two heteroatoms are connected by a bridge group W, and each of the three R ¹ groups contains one coordinating heteroatom. Preferably, the coordinating heteroatoms are nitrogen atoms.

Ligand L of the formula (C) includes at least one optionally substituted heteroaryl group in each of the three R ¹ groups. The heteroaryl group is preferably a pyridin-2-yl group, in particular a methyl or ethyl substituted pyridin-2-yl group. The heteroaryl group is bonded to the N atom in the formula (C), preferably via an alkylene group, more preferably a methylene group. Most preferably, the heteroaryl group is a 3-methylpyridin-2-yl group bonded to the N atom via methylene.

The R ² group in the formula (C) is a substituted or unsubstituted alkyl, aryl or arylalkyl group or an R ¹ group. However, in the above formula, R ^{2 is} preferably different from each of the R ¹ groups. Preferably, R ² is methyl, ethyl, benzyl, 2-hydroxyethyl or 2-methoxyethyl. More preferably, R ² is methyl or ethyl.

The bridge group W may be a substituted or unsubstituted alkylene group selected from —CH ₂ CH ₂ -, —CH ₂ CH ₂ CH ₂ -, —CH ₂ CH ₂ CH ₂ CH ₂ -, —CH ₂ —C ₆ H ₄ - CH ₂ -, -CH ₂ -C ₆ H ₁₀ -CH ₂ - and -CH ₂ -C ₁₀ H ₆ -CH ₂ - (where -C ₆ H ₄ -, C ₆ H ₁₀ -, C ₁₀ H ₆ - may represent ortho-, para- or meta-C ₆ H ₄ -, C ₆ H ₁₀ -, C ₁₀ H ₆ -). The bridge group W is preferably an ethylene or 1,4-butylene group, more preferably an ethylene group.

V is preferably substituted pyridin-2-yl, especially methyl substituted or ethyl substituted pyridin-2-yl, most preferably V is 3-methylpyridin-2-yl.

Examples of preferred ligands of formula (C) in their simplest form include

N-methyl-N, N ’, N’-tris (3-methylpyridin-2-ylmethyl) ethylene-1,2-diamine;

N-ethyl-N, N ’, N’-tris (3-methylpyridin-2-ylmethyl) ethylene-1,2-diamine;

N-benzyl-N, N ’, N’-tris (3-methylpyridin-2-ylmethyl) ethylene-1,2-diamine;

N- (2-hydroxyethyl) -N, N’, N’-tris (3-methylpyridin-2-ylmethyl) ethylene-1,2-diamine;

N- (2-methoxyethyl) -N, N’, N’-Tris (3-methylpyridin-2-ylmethyl) ethylene-1,2-diamine;

N-methyl-N, N ’, N’-tris (5-methylpyridin-2-ylmethyl) ethylene-1,2-diamine;

N-ethyl-N, N ’, N’-tris (5-methylpyridin-2-ylmethyl) ethylene-1,2-diamine;

N-benzyl-N, N ’, N’-tris (5-methylpyridin-2-ylmethyl) ethylene-1,2-diamine;

N- (2-hydroxyethyl) -N, N ’, N’-tris (5-methylpyridin-2-ylmethyl) ethylene-1,2-diamine;

N- (2-methoxyethyl) -N, N’, N’-tris (5-methylpyridin-2-ylmethyl) ethylene-1,2-diamine;

N-methyl-N, N ’, N’-tris (3-ethylpyridin-2-ylmethyl) ethylene-1,2-diamine;

N-ethyl-N, N ’, N’-tris (3-ethylpyridin-2-ylmethyl) ethylene-1,2-diamine;

N-benzyl-N, N ’, N’-tris (3-ethylpyridin-2-ylmethyl) ethylene-1,2-diamine;

N- (2-hydroxyethyl) -N, N’, N’-tris (3-ethylpyridin-2-ylmethyl) ethylene-1,2-diamine;

N- (2-methoxyethyl) -N, N’, N’-tris (3-ethylpyridin-2-ylmethyl) ethylene-1,2-diamine;

N-methyl-N, N ’, N’-tris (5-ethylpyridin-2-ylmethyl) ethylene-1,2-diamine;

N-ethyl-N, N ’, N’-tris (5-ethylpyridin-2-ylmethyl) ethylene-1,2-diamine;

N-benzyl-N, N ’, N’-tris (5-ethylpyridin-2-ylmethyl) ethylene-1,2-diamine and

N- (2-methoxyethyl) -N, N’, N’-tris (5-ethylpyridin-2-ylmethyl) ethylene-1,2-diamine.

More preferred ligands are

N-methyl-N, N ’, N’-tris (3-methylpyridin-2-ylmethyl) ethylene-1,2-diamine;

N-ethyl-N, N ’, N’-tris (3-methylpyridin-2-ylmethyl) ethylene-1,2-diamine;

N-benzyl-N, N ’, N’-tris (3-methylpyridin-2-ylmethyl) ethylene-1,2-diamine;

N- (2-hydroxyethyl) -N, N’, N’-tris (3-methyl-pyridin-2-ylmethyl) ethylene-1,2-diamine and

N- (2-methoxyethyl) -N, N’, N’-tris (3-methyl-pyridin-2-ylmethyl) ethylene-1,2-diamine.

The most preferred ligands are

N-methyl-N, N ’, N’-tris (3-methyl-pyridin-2-ylmethyl) ethylene-1,2-diamine;

N-ethyl-N, N ’, N’-tris (3-methyl-pyridin-2-ylmethyl) ethylene-1,2-diamine.

The metal M in the formula (A) is preferably Fe or Mn, more preferably Fe.

The coordinating group X in the formula (A) may preferably be selected from R ⁶ OH, NR $\genfrac{}{}{0ex}{}{\text{6}}{\text{3}}$ , R ⁶ OO ^- , R ⁶ S ^- , R ⁶ O ^- , R ⁶ COO ^- , OCN ^- , SCN ^- , N $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , CN ^- , F ^- , Сl ^- , Br ^- , I ^- , O ^2- , NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{2}}$ SO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{4}}$ , SO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{3}}$ , PO $\genfrac{}{}{0ex}{}{\text{3-}}{\text{4}}$ and N aromatic donors selected from pyridines, pyrazines, pyrazoles, pyrroles, imidazoles, benzimidazoles, pyrimidines, triazoles and thiazoles, wherein R ^{6 is} selected from hydrogen, optionally substituted alkyl, and optionally substituted aryl. X may also be an LMO ^- or LMOO ^- product, where M is a transition metal, and L is the ligand described above. The coordinating product X is preferably selected from CH ₃ CN, H ₂ O, F ^- , Cl ^- , Br ^- , UN ^- , R ⁶ COO ^- , R ⁶ O ^- , LMO ^- and LMOO ^- , where R ⁶ is hydrogen or optionally substituted phenyl, naphthyl or C ₁ -C ₄ alkyl.

The counterions Y in formula (A) balance the charge z on the complex formed by the ligand L, the metal M and the coordinating product X. Thus, if the charge z is positive, then Y can be an anion, such as R ⁷ COO ^- , BPh $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ ClO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ Bf $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , PF $\genfrac{}{}{0ex}{}{\text{-}}{\text{6}}$ R ⁷ SO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ R ⁷ SO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ SO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{4}}$ NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , F ^- , Cl ^- , Br ^- or I ^- , wherein R ⁷ is 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 counterions Y include ions that promote the formation of storage-stable solids. Preferred counterions for preferred metal complexes are selected from R ⁷ COO ^- , ClO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ Bf $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , PF $\genfrac{}{}{0ex}{}{\text{-}}{\text{6}}$ R ⁷ SO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ (in particular CF ₃ SO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ ), R ⁷ SO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ SO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{4}}$ NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , F ^- , Cl -, Br ^- or I ^- , where R ⁷ represents hydrogen or optionally substituted phenyl, naphthyl or C ₁ -C ₄ -alkyl.

An essential point is the formation of complex (A) by any suitable means, including in situ formation, the complex precursors being converted into the active complex of the general formula (A) under storage or use. The complex is preferably formed as a well-defined complex or in a solvent mixture comprising a metal salt M and a ligand L or a ligand L-forming product. Alternatively, the catalyst may be formed in situ from suitable precursors for the complex, for example, in a solution or dispersion containing precursor materials. According to one such example, the active catalyst may be formed in situ in a mixture comprising a metal salt of M and a ligand L or a ligand of an L-forming product in a suitable solvent. Thus, for example, if M is iron, then its salt, such as FeSO ₄ , can be mixed in solution with the ligand L or the ligand L-forming product, forming an active complex. According to another such example, the ligand L or the ligand L-forming product can be mixed with metal ions M present in the substrate or washing liquid, forming an active catalyst in situ. Suitable ligand L-forming products include metal-free compounds or metal coordination complexes including ligand L, and can be replaced by metal ions M to form an active complex in accordance with formula (A).

Therefore, in alternative fourth and fifth specific embodiments of the second embodiment, the organic substance is a compound of general formula (D)

[{M ' _a L} _b X _c ] ^z Y _q

in which M ’is hydrogen or a metal selected from Ti, V, Co, Zn, Mg, Ca, Sr, Ba, Na, K and Li;

X is a coordinating product;

a is an integer from 1 to 5;

b is an integer from 1 to 4;

c = 0 or an integer from 0 to 5;

z represents the charge of the compound and is equal to an integer that can be positive, 0 or negative;

Y is a counterion, a species which depends on the charge of the compound;

q = z / [charge Y] and

L is a five-tooth ligand of the above general formulas (B) or (C).

In a fourth specific embodiment of the first embodiment, the organic substance comprises a macrocyclic ligand of the formula (E)

where each of Z ¹ and Z ² independently selected from structures of a monocyclic or polycyclic ring, optionally containing one or more heteroatoms, with each structure of the aromatic ring substituted by one or more substituents;

Y ¹ and Y ^{2 are} independently selected from C, N, O, Si, P, and S atoms;

A ¹ and A ^{2 are} independently selected from hydrogen, alkyl, alkenyl and cycloalkyl, with the last three compounds optionally substituted with one or more groups selected from hydroxy, aryl, heteroaryl, sulfonate, phosphate, electron-releasing and electron-removing groups, and groups of formulas (G ¹ ) (G ² ) N-, G ³ OC (О) -, G ³ O- and G ³ C (О) -, where each of G ¹ , G ² and G ^{3 is} independently selected from hydrogen, alkyl, as well as electron-giving and / or removing groups (in addition to the groups contained in the above compounds);

i and j are selected from 0, 1 and 2, completing the valency of the groups Y ¹ and Y ² ;

each of Q ¹ -Q ⁴ , independently from each other, is selected from groups of the formula

where 10> a + b + c> 2, a d> = 1;

each of Y ^{3 is} independently selected from —O—, —S—, —SO—, —SO ₂ -, - (G ¹ ) N- (where G ¹ has the above meanings), —C (O) -, arylene, heteroarylene , -P- and P (O) -;

each of A ³ -A ^{6 is} independently selected from the groups indicated above for A ¹ and A ² , and

where any two or more of A ¹ -A ⁶ together form a bridging group, provided that if A ¹ and A ² are connected without simultaneously binding to any of A ³ -A ^{6 as well} , then the bridging group connecting A ¹ and A ² must contain at least one carbonyl group.

In ligands of formula (E), unless otherwise indicated, all alkyl, hydroxyalkylalkoxy and alkenyl groups preferably have from 1 to 6, more preferably from 1 to 4 carbon atoms.

Moreover, preferred electron-donating groups include alkyl (e.g. methyl), alkoxy (e.g. methoxy), phenoxy, as well as unsubstituted, monosubstituted and disubstituted amino groups. Preferred electron removal groups include nitro, carboxy, sulfonyl and halo groups.

Ligands of the formula (E) can be used as complexes with the corresponding metal or, in some cases, not as complexes. In the latter case, they can "rely" on the formation of a complex with a metal, which is in the form of a separate ingredient in a composition specially introduced for the presence of such a metal, or on the formation of a complex with a metal present as a trace element in tap water. However, when the ligand as such or as a complex carries a (positive) charge, the presence of a counterion is necessary. The ligand or complex can be obtained in the form of a neutral product, however, often for reasons of stability or ease of synthesis it is advisable to have a charged product with the corresponding anion.

Therefore, in an alternative fourth embodiment of the first embodiment, the ligand of formula (E) is paired with a counterion, which is represented by formula (F)

[H _x L] ^z Y _g

where H is a hydrogen atom;

Y is a counterion, the type of which depends on the charge of the complex;

x is an integer, so that in L there is a "protonation" of one or more nitrogen atoms;

z represents the charge of the complex and is an integer that can be positive or equal to 0;

q = z / [charge Y] and

L is a ligand of the above formula (E).

In a further alternative fourth embodiment of the first embodiment, the organic substance forms a metal complex of formula (G) based on the following pairing with an ion of formula (F)

[M _x L] ^z Y _q

where L, Y, x, z and q have the meanings indicated above for formula (F), and M is a metal selected from manganese in the oxidation state of II-V, iron II-V, copper I-III, cobalt I-III nickel I-III, chromium II-VI, tungsten IV-VI, palladium V, ruthenium II-IV, vanadium III-IV and molybdenum IV-VI.

Especially preferred are complexes of formula (G), where M is manganese, cobalt, iron or copper.

In a preferred fourth specific embodiment of the first embodiment, the organic substance forms a complex of formula (H)

where M represents an iron atom in the oxidation stage II or III, a manganese atom in the oxidation stage II, III, IV or V, a copper atom in the oxidation stage I, II or III, or a cobalt atom in the oxidation state II, III or IV, X - a group serving or not serving as a bridge between the iron atoms, Y is the counterion, with x and y> = 1, 0 = <n = <3, z is the charge of the metal complex, and p = z / is the charge of Y; R ₁ and R ₂ independently from one another - one or more ring substituents selected from hydrogen, as well as electron-giving and removing groups, R ₃ -R ₈ independently from each other - hydrogen, alkyl, hydroxyalkyl, alkenyl or their variants when substituted by one or several electron donor or acceptor groups.

For the avoidance of doubt, "= <" means "less than or equal to", and "> =" means "more than or equal to".

In the complex of formula (H), M represents an iron atom in an oxidation state of II or III, or a manganese atom in an oxidation state of II, III, IV or V. The oxidation state of M is preferably III.

When M is iron, the complex of formula (H) is preferably in the form of an iron salt (in an oxidized state) of dihalo-2,11-diazo [3,3] (2,6) pyridinophan, dihalo-4-methoxy-2, 11-diazo [3.3] (2.6) pyridinophan and mixtures thereof, especially in the form of chloride salt.

When M is manganese, the complex of formula (H) is preferably in the form of a manganese salt (in the oxidized state) N, N'-dimethyl-2,11-diazo [3.3] (2,6) pyridinophan, especially in the form of a salt of monohexafluorophosphate .

X is preferably selected from H ₂ O, OH ^- , O ^2- , SH ^- , S ^2- , SO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{4}}$ , NR ₉ R $\genfrac{}{}{0ex}{}{\text{-}}{\text{10}}$ , RCOO ^- , NR ₉ R ₁₀ R ₁₁ , Cl ^- , Br ^- , F ^- , N $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ and combinations thereof, where R ₉ , R ₁₀ , and R _{11 are} independently selected from —H, C _1-4 alkyl and aryl optionally substituted with one or more electron withdrawing and / or donor groups. More preferably, X is a halogen, especially a fluoride ion.

In the formulas (F), (G) and (H), the anionic counterion equivalent to Y is preferably selected from Cl ^- , Br ^- , I ^- , NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ ClO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , SCN ^- , PF $\genfrac{}{}{0ex}{}{\text{-}}{\text{6}}$ , PSO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , RSO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , CF ₃ SO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ BPh $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ and OAc ^- . The cationic counterionic equivalent is preferably absent.

In the formula (H), R ₁ and R _{2 are} preferably hydrogen. R ₃ and R _{4 are} preferably C _1-4 alkyl, especially methyl. Each of R ₅ -R _{8 is} preferably hydrogen.

According to x and y values, the aforementioned preferred iron or manganese catalysts of the formula (H) may be in the form of a monomer, dimer or oligomer. Without reference to any theory, it was suggested that in the raw material or composition of the detergent, the catalyst exists mainly or only in the form of a monomer, however, it can be converted into a dimer or even an oligomer in a washing solution.

In conventional detergent compositions, the level of organic matter is such that the level when used is from 1 μM to 50 mm, while the preferred level of use for home washing is from 10 to 100 μM. In industrial textile bleaching processes, a higher level may be required.

The aqueous medium preferably has a pH in the range from 6 to 13, more preferably from 6 to 11, even more preferably from 8 to 11 and most preferably from 8 to 10, in particular from 9 to 10.

The method in accordance with this invention has a specific application for bleaching with detergents, especially when washing with a wash. Accordingly, in another preferred embodiment, the method comprises using organic matter in a solution further comprising a surfactant, optionally together with a detergent component.

A bleaching fluid, for example, may contain surfactant in an amount of 10 to 50% by weight. The surface-active material can be obtained from natural substances (eg, soap), or a synthetic material selected from anionic, nonionic, amphoteric, zwitterionic, cationic active substances and mixtures thereof. Many suitable active substances manufactured for industrial purposes are described in the literature, for example, in “Surface Active Agents and Detergents”, Volumes I and II, by Schwartz, Perry and Berch.

Typical synthetic anionic surfactants are typically water-soluble alkali metal salts of organic sulfates and sulfonates having alkyl groups containing from about 8 to 22 carbon atoms, the term "alkyl" is used to mean the alkyl part of higher aryl groups. Examples of suitable synthetic anionic detergent compounds include sodium and ammonium alkyl sulfates, especially sulfates obtained by sulfating higher (C ₈ -C ₁₈ ) alcohols obtained, for example, from tall oil or coconut oil; sodium and ammonium alkyl (C ₉ -C ₂₀ ) -benzenesulfonates, especially sodium linear secondary alkyl (C ₁₀ -C ₁₅ ) -benzenesulfonates; sodium alkyl glyceryl ether sulfates, especially esters of higher alcohols derived from sulfates and sulfonates of tall oil or coconut oil fatty acid monoglyceride; reaction products of sodium and ammonium salts of sulfuric acid esters of alkylene oxide of higher (C ₉ -C ₁₈ ) fatty alcohol, especially ethylene oxide; reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralized with sodium hydroxide; methyltaurine fatty acid sodium and ammonium salts; alkane monosulfonates, for example, obtained by the reaction of alpha-olefins (C ₈ -C ₂₀ ) with sodium bisulfite and obtained by the reaction of paraffins with SO ₂ and Cl ₂ , and then hydrolysis with a base to obtain a random sulfonate; sodium and ammonium (C ₇ -C ₁₂ ) dialkyl sulfosuccinates and olefin sulfonates; this term is used to describe the material obtained by the reaction of olefins, in particular (C ₁₀ -C ₂₀ ) alpha olefins, with SO ₃ , and then neutralization and hydrolysis of the reaction product. Preferred anionic detergent compounds are sodium (C ₁₀ -C ₁₅ ) alkylbenzenesulfonates and sodium (C ₁₆ -C ₁₈ ) alkyl ethersulfonates.

Examples of suitable non-ionic surfactants, preferably applicable together with anionic surfactants, include, in particular, the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C ₆ -C ₂₂ ) phenols, usually 5-25 EO, those. 5-25 units of ethylene oxides per molecule, as well as condensation products of aliphatic (C ₈ -C ₁₈ ), primary or secondary, linear or branched alcohols with ethylene oxide, usually 2-30 EO. Other so-called non-ionic surfactants include alkyl polyglycosides, sugar esters, long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulfoxides.

Amphoteric or zwitterionic surfactants can also be used in the compositions of this invention, however this is usually undesirable due to their relatively high cost. When using amphoteric or zwitterionic detergent compounds, this usually occurs in small quantities in formulations based on the much more commonly used synthetic anionic and nonionic active substances.

The washing whitening liquid preferably comprises from 1 to 15 wt.% Of an anionic surfactant and from 10 to 40 wt.% Of a nonionic surfactant. According to a further preferred embodiment of the present invention, the active detergent system is free of soap from C ₁₆ -C ₁₂ fatty acids.

The bleaching liquid may also contain a detergent component, for example, in an amount of from about 5 to 80 wt.%, Preferably from about 10 to 60 wt.%.

The components can be selected from 1) calcium insulating materials, 2) precipitating materials, 3) calcium ion-exchange materials, and 4) mixtures thereof.

Examples of calcium insulating materials include alkali metal polyphosphates, such as sodium tripolyphosphate; nitrilotriacetic acid and its water soluble salts; alkali metal salts of carboxymethyloxy succinic acid, ethylenediaminetetraacetic acid, hydroxy succinic acid, mellitic acid, benzene polycarboxylic acids, citric acid, and polyacetal carboxylates as described in US-A-4144226 and US-A-4146495.

Examples of precipitating materials include orthophosphate and sodium carbonate.

Examples of calcium ion-exchange materials include various types of water-insoluble crystalline or amorphous aluminosilicates, the most famous of which are zeolites, for example zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y, as well as P-type zeolite, described in EP-A-0384070.

In particular, the whitening liquid may contain any of the organic and inorganic components, despite the fact that the phosphate components are preferably not used or are used only in very small quantities due to environmental pollution. Typical components useful in the present invention include, for example, sodium carbonate, calcite / carbonate, sodium nitrilotriacetic acid, sodium citrate, carboxymethyloxy malonate, carboxymethyloxy succinate and water-insoluble crystalline or amorphous aluminosilicate components, each of which can be used alone or as a main component in a mixture with small amounts of other components or polymers as juice components.

The composition preferably contains not more than 5 wt.% The carbonate component, expressed as sodium carbonate, more preferably from not more than 2.5 wt.% Essentially to zero, if the pH of the composition is in the lower alkaline range of up to 10.

In addition to the components already mentioned, the whitening liquid may contain any of the known additives in amounts commonly used in fabric detergent compositions. Examples of such additives include buffers such as carbonates, foaming accelerators such as alkanolamides, especially monoethanolamides derived from palm and coconut fatty acids; foaming absorbers such as alkyl phosphates and silicones; redeposition agents, such as carboxymethyl cellulose and alkyl or substituted alkyl cellulose ethers; stabilizers such as phosphonic acid derivatives (e.g., Dequest® type); fabric softening agents; inorganic salts and alkaline buffering agents, such as sodium sulfate and sodium silicate, and, usually in very small amounts, fluorescent agents; perfumes; enzymes such as proteases, cellulases, lipases, amylases and oxidases; germicides and dyes.

In addition to the above organic substances, transition metal sequestrants such as EDTA and phosphonic acid derivatives such as ethylene diamine tetra (methylene phosphonate) can also be included, for example, to improve the durability of sensitive ingredients such as enzymes, fluorescent agents and perfumes, but on condition that the whitening effect of the composition. However, the treatment composition containing organic matter is preferably substantially and more preferably completely devoid of transition metal sequestrants (other than organic matter).

Although this invention is based on the catalytic bleaching of a substrate with atmospheric oxygen or air, small amounts of hydrogen peroxide or those based on peroxide or its constituent systems may be included in the treatment composition if desired. However, preferably, the composition is devoid of peroxide bleach or peroxide-based or whitening systems forming it.

The invention is further illustrated by the following non-limiting examples.

Example 1

This example describes the synthesis of a catalyst in accordance with formula (A).

(i) Preparation of MeN4Py Ligand

The N4Py HClO ₄ precursor is prepared as follows.

Ethanol (15 ml), concentrated ammonia solution (15 ml) and NH ₄ OAc (1.21 g, 15.8 mmol) were added to pyridyl ketone oxime (3 g, 15.1 mmol). The solution is heated to reflux. 4.64 g of Zn are added in small portions to this solution. After adding all of Zn, the mixture was refluxed for 1 hour and allowed to cool to room temperature. The solution was filtered and water (15 ml) was added to it. Solid NaOH was added until pH >> 10 and the solution was extracted with CH ₂ Cl ₂ (3 × 20 ml). The organic layers were dried over Na ₂ SO ₄ and evaporated to dryness. Bis (pyridin-2-yl) methylamine (2.39 g, 12.9 mmol) is obtained as a colorless oil with a yield of 86% and having the following analytical characteristics.

¹ H NMR (360 MHz, CDCl ₃ ): δ 2.64 (s, 2H, NH ₂ ), 5.18 (s, 1H, CH), 6.93 (m, 2H, pyridine), 7.22 (m, 2H, pyridine), 7.41 (m, 2H, pyridine); 8.32 (m, 2H, pyridine).

¹³ C NMR (CDCl ₃ ): δ 62.19 (CH), 121.73 (CH), 122.01 (CH), 136.56 (CH), 149.03 (CH), 162.64 (Cq).

Hydrochloride (4.06 g, 24.8 mmol) was added to picolyl chloride at 0 ° C, 4.9 ml of a 5 N NaOH solution. This emulsion at 0 ° C. is added via syringe to bis (pyridin-2-yl) methylamine (2.3 g, 12.4 mmol). To this mixture was again added 5 N NaOH solution. After warming to ambient temperature, the mixture was vigorously stirred for 40 hours. The mixture was placed in an ice bath and HC1O _{4 was} added to it until a pH <1 was obtained, and a solid brown solid precipitated, which was collected by filtration and recrystallized from water. With stirring, this mixture is cooled to ambient temperature, whereupon a light brown solid precipitates, which is collected by filtration, washed with cold water and dried in air (1.47 g).

From 0.5 g of the N4Py perchlorate salt prepared as described above, a free amine is obtained by precipitating a 2 N NaOH salt and then extracting with CH ₂ Cl ₂ . 20 ml of dry tetrahydrofuran freshly distilled from LiAlH ₄ are added to the free amine in an argon atmosphere. The mixture is stirred and cooled to −70 ° C. using an alcohol / dry ice bath. Then add 1 ml of a 2.5 N solution of butyllithium in hexane, immediately staining the mixture in dark red. The mixture was allowed to warm to -20 ° C, after which 0.1 ml of methyl iodide was added. The temperature is maintained at -10 ° C for 1 hour. Then, 0.5 g of ammonium chloride was added and the mixture was evaporated in vacuo. Water was added to the residue, extracting the aqueous layer with dichloromethane. The dichloromethane layer was dried on sodium sulfate, filtered and evaporated to give a 0.4 g residue. The residue was purified by crystallization from ethyl acetate and hexane to obtain 0.2 g of a creamy powder (50% yield) having the following analytical characteristics.

¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) 2.05 (s, 3H, CH ₃ ), 4.01 (s, 4H, CH ₃ ), 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).

¹³ C NMR (100.55 MHz, CDCl ₃ ): δ (ppm) 21.7 (CH ₃ ), 58.2 (CH ₂ ), 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 (CH ₃ CN)] (ClO ₄ ) ₂ , Fe (MeN4Py)

To a solution of 0.27 g of MeN4Py in 12 ml of a mixture of 6 ml of acetonitrile and 6 ml of methanol, 350 mg of Fe (ClO ₄ ) _{2 ·} 6H ₂ O is added, after which the mixture immediately turns dark red. Then, 0.5 g of sodium perchlorate is added to the mixture, causing an immediate formation of an orange-red precipitate. After five minutes of stirring and ultrasonic treatment, the precipitate was separated by filtration and dried in vacuo at 50 ° C. Thus, 350 mg of an orange-red powder was obtained in a yield of 70% and having the following analytical characteristics.

¹ H NMR (400 MHz, CD ₃ CN): δ (ppm) 2.15, (CH ₃ CN) 2.28 (s, 3H, CH ₃ ), 4.2 (ab, 4H, CH ₂ ), 7.05 (d, 2H, pyridine ), 7.38 (m, 4H, pyridine), 7.71 (2t, 4H, pyridine), 7.98 (t, 2H, pyridine), 8.96 (d, 2H, pyridine), 9.06 (m, 2H, pyridine).

UV / Vis (acetonitrile) [λ max, nm (ε, M ^-1 cm ^-1 )]: 381 (8400), 458 nm (6400).

Calculated for C ₂₅ H ₂₆ Cl ₂ FeN ₆ O ₈ ,%: C 46.11; H 3.87; N, 12.41; C1 10.47; Fe 8.25.

Found%: C 45.49; H 3.95; N, 12.5; Cl 10.7; Fe 8.12.

Mass spectrum (taper voltage 17V in CH ₃ CN): m / z 218.6 [MeN4PyFe] ²⁺ ; 239.1 [MeN4PyFeCH ₃ CN] ²⁺ .

Example 2

This example describes the synthesis of a catalyst in accordance with formula (A).

(i) Synthesis of BzN4Py Ligand

To 1 g of the N4Py ligand obtained in accordance with the above description, 20 ml of dry tetrahydrofuran freshly distilled from LiAlH ₄ are added under argon atmosphere. The mixture is stirred and cooled to −70 ° C. using an alcohol / dry ice bath. After that, add 2 ml of a 2.5 N solution of butyllithium in hexane, immediately staining the mixture in dark red. The mixture is allowed to warm to -20 ° C, after which 0.4 ml of benzyl bromiodide is added. The mixture is allowed to warm to 25 ° C and stirring is continued overnight. Then, 0.5 g of ammonium chloride was added and the mixture was evaporated in vacuo. Water was added to the residue, extracting the aqueous layer with dichloromethane. The dichloromethane layer was dried on sodium sulfate, filtered and evaporated to give a brown oil residue weighing 1 g. According to NMR spectroscopy, the product was not pure but did not contain the starting material (N4Py). The residue is used without further purification.

(ii) Synthesis of the complex [(BzN4Py) Fe (CH ₃ CN)] (ClO ₄ ) ₂ , Fe (BzN4Py)

To a solution of 0.2 g of the residue obtained by the above procedure in 10 ml of a mixture of 5 ml of acetonitrile and 5 ml of methanol, 100 mg of Fe (ClO ₄ ) ₂ .6H ₂ O is added, after which the mixture immediately turns dark red . Then, 0.25 g of sodium perchlorate was added to the mixture, and ethyl acetate was allowed to diffuse into the mixture overnight. The resulting red crystals are separated by filtration and washed with methanol. Thus, 70 mg of red powder is obtained having the following analytical characteristics.

¹ H NMR (400 MHz, CD ₃ CN): δ (ppm) 2.12, (s, 3H, CH ₃ CN), 3.65 + 4.1 (ab, 4H, CH ₂ ), 4.42 (s, 2H, CH ₂ -benzyl ), 6.84 (d, 2H, pyridine), 7.35 (m, 4H, pyridine), 7.45 (m, 3H, benzene), 7.65 (m, 4H, benzene + pyridine), 8.08 (m, 4H, pyridine), 8.95 (m, 4H, pyridine).

UV / Vis (acetonitrile) [λ max, nm (ε, M ^-1 cm ^-1 )]: 380 (7400), 458 (5500).

Mass spectrum (taper voltage 17V in CH ₃ CN): m / z 256.4 [BzN4Py] ²⁺ ; 612 [BzN4PyFeC1O ₄ ] ⁺ .

Example 3

This example describes the synthesis of catalysts in accordance with formula (C).

Unless otherwise indicated, all reactions are carried out in a nitrogen atmosphere. Unless otherwise indicated, all reagents and solvents are obtained from Aldrich or Across and are used in finished form. Before use as a solvent for elution, petroleum ether 40-60 is subjected to distillation using a rotary evaporator. Flash column chromatography was performed using Merck silica gel 60 or 90 alumina (activity II-III according to Brockman). Unless otherwise indicated, ¹ H NMR (300 MHz) and ¹³ C NMR (75 MHz) are recorded in CDCl ₃ . Multiplicity is denoted by conventional abbreviations, with p meaning "quintet".

Synthesis of starting materials for ligand synthesis

Synthesis of N-benzylaminoacetonitrile

N-Benzylamine (5.35 g, 50 mmol) was dissolved in water: methanol (50 ml, 1: 4). Hydrochloric acid (aq., 30%) is added until the pH reaches 7.0. NaCN (2.45 g, 50 mmol) was added. After cooling to 0 ° C. formalin (aq., 35%, 4.00 g, 50 mmol) was added. The reaction is monitored by thin layer chromatography (TLC) (alumina; EtOAc.:Et ₃ N = 9: 1) until benzylamine is detected. After that, methanol is evaporated in vacuo, and the remaining oil is "dissolved" in water. The aqueous phase is extracted with methylene chloride (3 × 50 ml). The organic layers were collected and the solvent was removed in vacuo. The residue was purified by Kugelrohr distillation (p = 20 mmHg, T = 120 ° C) to give N-benzylaminoacetonitrile (4.39 g, 30 mmol, 60%) as a colorless oil.

¹ H NMR: δ 7.37 - 7.30 (m, 5H), 3.94 (s, 2H), 3.57 (s, 2H), 1.67 (br s, 1H).

¹³ C NMR: δ 137.74, 128.58, 128.46, 128.37, 127.98, 127.62, 117.60, 52.24, 36.19.

Synthesis of N-ethylaminoacetonitrile

This synthesis is carried out similarly to the synthesis described for N-benzylaminoacetonitrile, while detection is carried out by immersing the TLC plate in a KMnO ₄ solution and heating it until bright spots appear. Using ethylamine (2.25 g, 50 mmol) as the starting material, pure N-ethylaminoacetonitrile (0.68 g, 8.1 mmol, 16%) was obtained as a yellowish oil.

¹ H NMR: δ 3.60 (s, 2H), 2.78 (q, J = 7.1, 2H), 1.22 (br, s, 1H), 1.14 (t, J = 7.2, 3H).

¹³ C NMR: δ 117.78, 43.08, 37.01, 14.53.

Synthesis of N-Ethylethylene-1,2-Diamine

This synthesis is carried out in accordance with Hageman., J. Org. Chem .; 14; 1949; 616, 654 using N-ethylaminoacetonitrile as a starting material.

Synthesis of N-benzylethylene-1,2-diamine

Sodium hydroxide (890 mg, 22.4 mmol) is dissolved in ethanol (96%, 20 ml), while the dissolution process continues for almost 2 hours. N-benzylaminoacetonitrile (4, 2.92 g, 20 mmol) and Raney nickel (approx. 0.5 g) are added to the solution. Hydrogen pressure (p = 3 atm) is applied until its absorption ceases. The mixture is filtered through celite, washing the residue with ethanol, and the filter should not dry, since Raney nickel is relatively pyrophoric. Celite containing Raney nickel is decomposed by adding the mixture to dilute acid and causing gas formation. Ethanol was evaporated in vacuo, and the residue was dissolved in water. After adding the base (aq. NaOH, 5 N), the product isolated as an oil was extracted with chloroform (3 × 20 ml). After evaporation of the solvent in vacuo, ¹ H NMR indicates the presence of benzylamine. The separation is carried out using column chromatography (silica gel; MeOH: EtOAc: Et ₃ N = 1: 8: 1) to obtain benzylmethyl, and then a mixture of a solution of MeOH: EtOAc: Et ₃ N = 5: 4: 1. Detection is carried out using alumina in the form of a solid phase in TLC, while obtaining pure N-benzylethylene-1,2-diamine (2.04 g, 13.6 mmol, 69%).

¹ H NMR: δ 7.33-7.24 (m, 5H), 3.80 (s, 2H), 2.82 (t, J = 5.7, 2H), 2.69 (t, J = 5.7, 2H), 1.46 (br s, 3H) .

¹³ C NMR: δ 140.37, 128.22, 127.93, 126.73, 53.73, 51.88, 41.66.

Synthesis of 2-acetoxymethyl-5-methylpyridine

2,5-Lutidine (31.0 g, 290 mmol), acetic acid (180 ml) and hydrogen peroxide (30 ml, 30%) are heated at 70-80 ° C for three hours. Hydrogen peroxide (24 ml, 30%) was added and the resulting mixture was heated for 16 hours at 60-70 ° C. Most of the mixture, consisting of (probably) hydrogen peroxide, water, acetic acid and peracetic acid, was removed in vacuo (rotary evaporator water bath at 50 ° C to p = 20 mbar). The resulting N-oxide-containing mixture was added dropwise to acetic anhydride heated by reflux. This highly exothermic reaction is controlled by reducing speed. After heating under reflux for one hour, methanol was added dropwise. This reaction is highly exothermic. The resulting mixture was heated under reflux for another 30 minutes. After evaporation of methanol (rotary evaporator, 50 ° C to p = 20 mbar), the resulting mixture was purified by Kugelrohr distillation (p = 20 mmHg, T = 150 ° C). A clear oil is still obtained containing acetic acid, which is removed by extraction (CH ₂ Cl ₂ , NaHCO ₃ (sat.)) To give pure 2-acetoxymethyl-5-methylpyridine acetate (34.35 g, 208 mmol, 72%) in as a yellowish oil.

¹ H NMR: δ 8.43 (s, 1H), 7.52 (dd, J = 7.8, J = 1.7, 1H), 7.26 (d, J = 7.2, 1H), 5.18 (s, 2H), 2.34 (s, 3H ), 2.15 (s, 3H).

¹³ C NMR: δ 170.09, 152.32, 149.39, 136.74, 131.98, 121.14, 66.31, 20.39, 17.66.

Synthesis of 2-acetoxymethyl-5-ethylpyridine

This synthesis is carried out analogously to the synthesis described for 2-acetoxymethyl-5-methylpyridine. Using 5-ethyl-2-methylpyridine (35.10 g, 290 mmol) as the starting material, pure 2-acetoxymethyl-5-ethylpyridine (46.19 g, 258 mmol, 89%) was obtained as a yellowish oil.

¹ H NMR: δ 8.47 (s, 1 H), 7.55 (d, J = 7.8, 1H), 7.29 (d, J = 8.1, 1H), 2.67 (q, J = 7.8, 2H), 2.14 (s, 3H), 1.26 (t, J = 7.77, 3H).

¹³ C NMR: δ 170.56, 152.80, 149.11, 138.47, 135.89, 121.67, 66.72, 25.65, 20.78, 15.13.

Synthesis of 2-acetoxymethyl-3-methylpyridine

This synthesis is carried out analogously to the synthesis described for 2-acetoxymethyl-5-methylpyridine. The only difference is Kugelrohr reverse distillation and extraction. In accordance with ¹ H NMR, a mixture of acetate and the corresponding alcohol is obtained. Using 2,3-picoline (31.0 g, 290 mmol) as the starting material, pure 2-acetoxymethyl-3-methylpyridine (46.19 g, 258 mmol, 89%, calculated as pure acetate) is obtained as yellowish oils.

¹ H NMR: δ 8.45 (d, J = 3.9, 1H), 7.50 (d, J = 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-hydroxymethyl-5-methylpyridine

2-Acetoxymethyl-5-methylpyridine (30 g, 182 mmol) was dissolved in hydrochloric acid (100 ml, 4 N). The mixture is heated under reflux until TLC (silica gel; triethylamine: ethyl acetate: petroleum ether (40-60) = 1: 9: 19) shows a complete absence of acetate (usually within 1 hour). The mixture was cooled, the pH was adjusted to pH> 11, extracted with dichloromethane (3 × 50 ml) and the solvent was removed in vacuo. Pure 2-hydroxymethyl-5-methylpyridine (18.80 g, 152 mmol, 84%) was obtained by distillation of Kugelrohr (p = 20 mmHg, T = 130 ° C) as a yellowish oil.

¹ H NMR: δ 8.39 (s, 1H), 7.50 (dd, J = 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).

¹³ C NMR: δ 156.67, 148.66, 137.32, 131.62, 120.24, 64.12, 17.98.

Synthesis of 2-hydroxymethyl-5-ethylpyridine

This synthesis is carried out analogously to the synthesis described for 2-hydroxymethyl-5-methylpyridine. Using 2-acetoxymethyl-5-ethylpyridine (40 g, 223 mmol) as the starting material, pure 2-hydroxymethyl-5-ethylpyridine (26.02 g, 189 mmol, 85%) was obtained as a yellowish oil.

¹ H NMR: δ 8.40 (d, J = 1.2, 1H), 7.52 (dd, J = 8.0, J = 2.0, 1H), 7.18 (d, J = 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).

¹³ C NMR: δ 156.67, 148.00, 137.87, 136.13, 120.27, 64.07, 25.67, 15.28.

Synthesis of 2-hydroxymethyl-3-methylpyridine

This synthesis is carried out analogously to the synthesis described for 2-hydroxymethyl-5-methylpyridine. Using 2-acetoxymethyl-3-methylpyridine (25 g (calculated for the mixture), 152 mmol), pure 2-hydroxymethyl-3-methylpyridine (15.51 g, 126 mmol, 83%) was obtained as a yellowish oil.

¹ H NMR: δ 8.40 (d, J = 4.5, 1H), 7.47 (d, 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, 3H).

¹³ C NMR: δ 156.06, 144.97, 137.38, 129.53, 121.91, 61.38, 16.30.

(i) Synthesis of ligands

Synthesis of N-methyl-N, N ’, N’-Tris (pyridin-2-ylmethyl) ethylene-1,2-diamine (L1)

Ligand L1 (comparative) is prepared as described by Bernal, Ivan; Jensen Inge Margrethe; Jensen, Kenneth W. .; McKenzie, Christine I .; Toftlund., Hans; Tuchagues, Jean-Pierre; J, Chem. Soc. Dalton Trans .; 22; 1995; 3667-3676.

Synthesis of N-methyl-N, N ’, N’-Tris (3-methylpyridin-2-ylmethyl) ethylene-1,2-diamine (L2, MeTrilen)

2-hydroxymethyl-3-methylpyridine (5.00 g, 40.7 mmol) was dissolved in dichloromethane (30 ml). Thionyl chloride (30 ml) was added dropwise upon cooling (ice bath). The resulting mixture was stirred for 1 hour and the solvents were removed in vacuo (rotary evaporator, up to p = 20 mmHg, T = 50 ° C). Dichloromethane (25 ml) was added to the resulting mixture. Then, NaOH (5 N aq.) Was added dropwise until the pH reached pH (water) ≥ 11. The onset of the reaction was quite rapid, since part of the thionyl chloride was still present. N-methylethylene-1,2-diamine (502 mg, 6.8 mmol) and additional NaOH (5 N, 10 ml) were added. The reaction mixture was stirred at room temperature for 45 hours. The mixture was poured into water (200 ml) and the pH was checked (if pH was not ≥ 14, then NaOH (aq., 5 N) was added. The reaction mixture was extracted with dichloromethane (3 or 4 × 50 ml until TLC showed no product). The combined organic phases are dried and the solvent removed in vacuo. Purification is carried out as described above to obtain N-methyl-N, N ', N'-tris (3-methylpyridin-2-ylmethyl) ethylene-1,2- diamine in the form of a yellowish oil. Purification is carried out using column chromatography (alumina 90 (Brockman activity II-III); three tylamine: ethyl acetate: petroleum ether (40-60) = 1: 9: 10) until the impurities are removed according to TLC (alumina, the same solvent for elution, Rf≈ 0.9). The compound is subjected elution using ethyl acetate: triethylamine, 9: 1, and obtaining N-methyl-N, N ', N'-tris (3-methylpyridin-2-ylmethyl) ethylene-1,2-diamine (L2, 1,743 g, 4, 30 mmol, 63%).

¹ H NMR: δ 8.36 (d, J = 3.0, 3H), 7.40-7.37 (m, 3H), 7.11-7.06 (m, 3H), 3.76 (s, 4H), 3.48 (s, 2H), 2.76- 2.71 (m, 2H), 2.53-2.48 (m, 2H), 2.30 (s, 3H), 2.12 (s, 6H), 2.05 (s, 3H).

¹³ C NMR: δ 156.82, 156.77, 145.83, 145.67, 137.61, 133.14, 132.72, 122.10, 121.88, 62.32, 59.73, 55.19, 51.87, 42.37, 18.22, 17.80.

Synthesis of N-ethyl-N, N ’, N’-tris (3-methylpyridin-2-ylmethyl) ethylene-1,2-diamine (L3, Etrilene)

This synthesis is carried out similarly to the synthesis described for L2. Using 2-hydroxymethyl-3-methylpyridine (25.00 g, 203 mmol) and N-ethylene-1,2-diamine (2.99 g, 34.0 mmol) as starting materials, N-ethyl-N is obtained. N ', N'-Tris (methylpyridin-2-ylmethyl) ethylene-1,2-diamine (L3, 11.49 g, 28.5 mmol, 84%). Column chromatography was performed (alumina; Et ₃ N: EtOAc: petroleum ether (40-60) = 1: 9: 30 and then Et ₃ N: EtOAc = 1: 9).

¹ H NMR: δ 8.34-8.30 (m, 3H), 7.40-7.34 (m, 3H), 7.09-7.03 (m, 3H), 3.71 (s, 4H), 3.58 (s, 2H), 2.64-2.59 ( m, 2H), 2.52-2.47 (m, 2H), 2.43-2.36 (m, 2H), 2.31 (s, 3H), 2.10 (s, 6H), 0.87 (t, J = 7.2, 3H).

¹³ C NMR: δ 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, 17.80, 11.36.

Synthesis of N-benzyl-N, N ’, N’-Tris (3-methylpyridin-2-ylmethyl) ethylene-1,2-diamine (L4, BzTrilen)

This synthesis is carried out similarly to the synthesis described for L2. Using 2-hydroxymethyl-3-methylpyridine (3.00 g, 24.4 mmol) and N-benzylethylene-1,2-diamine (610 mg, 4.07 mmol) as starting materials, N-benzyl-N, N ', N'-Tris (3-methylpyridin-2-ylmethyl) ethylene-1,2-diamine (L4, 1.333 g, 2.93 mmol, 72%). Column chromatography was performed (alumina; Et ₃ N: EtOAc: petroleum ether (40-60) = 1: 9: 10).

¹ H NMR: δ 8.33-8.29 (m, 3H), 7.37-7.33 (m, 3H), 7.21-7.03 (m, 8H), 3.66 (s, 4H), 3.60 (s, 2H), 3.42 (s, 2H), 2.72-2.67 (m, 2H), 2.50-2.45 (m, 2H), 2.23 (s, 3H), 2.03 (s, 6H).

¹³ C NMR: δ 157.17, 156.96, 145.83, 145.78, 139.29, 137.91, 137.80, 133.45, 133.30, 128.98, 127.85, 126.62, 122.28, 122.22, 59.99, 58.83, 51.92, 51.54, 18.40, 17.95.

Synthesis of N-hydroxyethyl-N, N’, N’-Tris (3-methylpyridin-2-ylmethyl) ethylene-1,2-diamine (L5)

This synthesis is carried out analogously to the synthesis described for L6. Using 2-hydroxymethyl-3-methylpyridine (3.49 g, 28.4 mmol) and N-hydroxyethylethylene-1,2-diamine (656 mg, 6.30 mmol) as starting materials, N-hydroxyethyl was obtained after 7 days -N, N ', N'-Tris (3-methylpyridin-2-ylmethyl) ethylene-1,2-diamine (L5, 379 mg, 0.97 mmol, 14%).

¹ H NMR: δ 8.31-8.28 (m, 3H), 7.35-7.33 (m, 3H), 7.06-7.00 (m, 3H), 4.71 (br s, 1H), 3.73 (s, 4H), 3.61 (s , 2H), 3.44 (t, J = 5.1, 2H), 2.68 (s, 4H), 2.57 (t, J = 5.0, 2H), 2.19 (s, 3H), 2.10 (s, 6H).

¹³ C NMR: δ 157.01, 156.88, 145.91, 145.80, 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 N-methyl-N, N ’, N’-Tris (5-methylpyridin-2-ylmethyl) ethylene-1,2-diamine (L6)

2-hydroxymethyl-5-methylpyridine (2.70 g, 21.9 mmol) was dissolved in dichloromethane (25 ml). Thionyl chloride (25 ml) was added dropwise upon cooling (ice bath). The resulting mixture was stirred for 1 hour and the solvents were removed in vacuo (rotary evaporator, up to p = 20 mmHg, T ± 35 ° C). The remaining oil is used directly in the synthesis of ligands, since it is known from the literature that free picolyl chlorides are somewhat unstable and highly lacrimatory. Dichloromethane (25 ml) and N-methylethylene-1,2-diamine (360 mg, 4.86 mmol) were added to the resulting mixture. Then NaOH (5 N, aq) was added dropwise. The onset of the reaction is quite rapid, as part of the thionyl chloride is still present. The aqueous layer was adjusted to pH 10 and an additional amount of NaOH (5 N, 4.38 ml) was added. The reaction mixture was stirred until the sample showed complete conversion (7 days). The reaction mixture was extracted with dichloromethane (3 × 25 ml). The combined organic phases are dried and the solvent removed in vacuo. Purification is carried out using column chromatography (alumina 90 (Brockmann activity II-III); triethylamine: ethyl acetate: petroleum ether (40-60) = 1: 9: 10) until the impurities are removed in accordance with TLC (alumina, the same solvent for elution, Rf≈ 0.9). The compound was eluted using ethyl acetate: triethylamine = 9: 1 to give N-methyl-N, N ', N'-tris (5-methylpyridin-2-ylmethyl) ethylene-1,2-diamine (L6, 685 mg, 1 , 76 mmol, 36%) as a yellowish oil.

¹ H NMR: δ 8.31 (s, 3H), 7.43-7.35 (m, 5H), 7.21 (d, J = 7.8, 1H), 3.76 (s, 4H), 3.56 (s, 2H), 2.74-2.69 ( m, 2H), 2.63-2.58 (m, 2H), 2.27 (s, 6H), 2.16 (s, 3H).

¹³ C NMR: δ 156.83, 156.43, 149.23, 149.18, 136.85, 136.81, 131.02, 122.41, 122.30, 63.83, 60.38, 55.53, 52.00, 42.76, 18.03.

Synthesis of N-methyl-N, N ’, N’-Tris (5-ethylpyridin-2-ylmethyl) ethylene-1,2-diamine (L7)

This synthesis is carried out analogously to the synthesis described for L6. Using 2-hydroxymethyl-5-ethylpyridine (3.00 g, 21.9 mmol) and N-methylethylene-1,2-diamine (360 mg, 4.86 mmol) as starting materials, after 7 days, N-methyl -N, N ', N'-Tris (5-ethylpyridin-2-ylmethyl) ethylene-1,2-diamine (L7, 545 mg, 1.26 mmol, 26%).

¹ H NMR: δ 8.34 (s, 3H), 7.44-7.39 (m, 5H), 7.26 (d, J = 6.6, 1H), 3.80 (s, 4H), 3.59 (s, 2H), 2.77-2.72 ( m, 2H), 2.66-2.57 (m, 8H), 2.18 (s, 3H), 1.23 (t, J = 7.5, 9H).

¹³ C NMR: δ 157.14, 156.70, 148.60, 148.53, 137.25, 135.70, 122.59, 122.43, 63.91, 60.48, 55.65, 52.11, 42.82, 25.73, 15.36.

(ii) Synthesis of metal-ligand complexes

Synthesis of N-methyl-N, N ', N'-Tris (3-methylpyridin-2-ylmethyl) ethylene-1,2-diamine iron chloride PF ₆ ([L2Fe (II) Cl] PF ₆ )

FeCl _{2 ·} 4H ₂ O (51.2 mg, 257 μmol) was dissolved in MeOH: H ₂ O = 1: 1 (2.5 ml). The solution was heated to 50 ° C. and N-methyl-N, N ′, N′-Tris (3-methylpyridin-2-ylmethyl) ethylene-1,2-diamine (L2, 100 mg, 257 μmol) in MeOH was added to it : H ₂ O = 1: 1 (2.0 ml). Then, NaPF ₆ (86.4 mg, 514 μmol) in H ₂ O (2.5 ml) was added dropwise. After cooling to room temperature, filtering and drying in vacuo (p = 0.05 mm Hg, T = room temperature), the complex [L2Fe (II) Cl] PF ₆ (149 mg, 239 μmol, 93%) in solid yellow substance.

¹ H NMR (CD ₃ CN, paramagnetic): δ 167.17, 142.18, 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, 3.43, 2.91, 2.05, 1.75, 1.58, 0.94, 0.53, -0.28, -1.25, -4.82, -18.97, -23.46.

Synthesis of N-ethyl-N, N ', N'-Tris (3-methylpyridin-2-ylmethyl) ethylene-1,2-diamine iron chloride (II). PF ₆ ([L3Fe (II) Cl] PF ₆ )

This synthesis is carried out analogously to the synthesis described for [L2Fe (II) Cl] PF ₆ . Using starting material N-ethyl-N, N ', N'-tris (3-methylpyridin-2-ylmethyl) ethylene-1,2-diamine (L3, 104 mg, 257 μmol), the complex [L3Fe (II ) Cl] PF ₆ (146 mg, 229 μmol, 89%) as a yellow solid.

¹ H NMR (CD ₃ CN, paramagnetic): δ 165.61, 147.20, 119.23, 112.67, 92.92, 63.14, 57.44, 53.20, 50.43, 47.80, 28.59, 27.09, 22.48, 8.55, 7.40, 3.63, 2.95, 2.75, 2.56, 2.26, 1.75, 1.58, 0.92, 0.74, -0.28, -1.68, -2.68, -12.36, -28.75.

Synthesis of N-benzyl-N, N ', N'-Tris (3-methylpyridin-2-ylmethyl) ethylene-1,2-diamine iron chloride (II). PF ₆ ([L4Fe (II) Cl] PF ₆ )

This synthesis is carried out analogously to the synthesis described for [L2Fe (II) Cl] PF ₆ . Using starting material N-benzyl-N, N ', N'-Tris (3-methylpyridin-2-ylmethyl) ethylene-1,2-diamine (L4, 119.5 mg, 257 μmol), a complex (172 mg, 229 μmol, 95%) as a yellow solid.

¹ H NMR (CD ₃ CN, paramagnetic): δ 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, 8.45, 7.69, 6.99, 6.01, 4.12, 2.89, 2.71, 1.93, 1.56, -0.28, -1.68, -2.58, -11.40, -25.32.

Example 4

This example describes the synthesis of a catalyst of formula (H)

where R ₂ -R ₈ = H; R ₁ = 4-MeO; x is 1; y = 1; z is 1; X = Cl, n = 2; Y = Cl ^- , p = 1.

(i) Synthesis of 2,11-diaz ligand [3.3.] - (4-methoxy) (2,6) pyridinophan ((4OMe) LN ₄ H ₂ )

4-Chloro-2,6-pyridyldimethyl ether (2)

A mixture of 4-hydroxy-2,6-pyridinedicarboxylic acid (12.2 g, 60 mmol) and PCl ₅ (41.8 g, 200 mmol) in 100 ml of CCl ₄ was refluxed until the evolution of Hcl ceased. Absolute methanol (50 ml) was slowly added. After cooling, all volatiles are removed. Then the mixture is poured into 200 ml of water and ice. Immediately crystallizing diester was collected by filtration (70%).

¹ H MNR (200 MHz, H ₂ O): δ 7.60 (2H, s), 4.05 (6H, s).

4-Methoxy-2,6-pyridinedimethanol (4)

Sodium metal (1 g, 44 mmol) was dissolved in 200 ml of dry methanol. Then 4-chloro-2,6-pyridyl dimethyl ether (9.2 g, 40 mmol) was added and the mixture was refluxed to give pure 4-methoxy-2,6-pyridyl dimethyl ether. To this solution, NaBH ₄ (9.1 g, 240 mmol) was added in small portions at room temperature, and the mixture was refluxed for 16 hours. Then acetone (30 ml) was added and the solution was refluxed for another 1 hour. After removal of all volatiles, the residue is heated with 60 ml of a saturated solution of NaHCO ₃ / Na ₂ CO ₃ . After dilution with 80 ml of water, the product is subjected to continuous extraction with CHCl ₃ for 2-3 days. Evaporation of CHCl ₃ afforded 83% 4-methoxy-2,6-pyridinadimethanol.

¹ H NMR (200 MHz, H ₂ O): δ 6.83 (2H, s), 5.30 (2H, s), 4.43 (4H, s), 3.82 (3H, s).

4-Methoxy-2,6-dichloromethylpyridine (5)

This synthesis is carried out in accordance with the description given in the literature.

N, N’-Ditosyl-2,11-diaz [3.3] - (4-methoxy) (2,6) pyridinophan

This procedure is similar to the procedure described in the literature. The resulting crude product is practically pure (95% yield).

¹ H NMR (CDCl ₃ , 250 MHz): 7.72 (4H, d, J = 7Hz), 7.4 (1H, t, J = 6Hz), 7.35 (4H, d, J = 7Hz), 7.1 (1H, d, J = 6Hz), 6.57 (2H, s), 4.45 (4H, s), 4.35 (4H, s), 3.65 (3H, s), 2.4 (6H, s).

2,11-Diaza [3.3] - (4-methoxy) (2,6) pyridinophan

This procedure is similar to the procedure described above. The resulting crude product was purified by chromatography (alumina, CH ₂ Cl ₂ / MeOH, 95: 5), yield 65%.

¹ H NMR (CDCl ₃ , 250 MHz): 7.15 (1H, t, J = 6Hz), 6.55 (1H, d, J = 6Hz), 6.05 (2H, s), 3.95 (4H, s), 3.87 (4H , s), 3.65 (3H, s).

Mass spectrum (EI): M ⁺ = 270 (100%).

(ii) Synthesis of the complex [Fe (4ОМеLN ₄ Н ₂ ) Cl ₂ ] Cl

270 mg of 2,11-diaz [3.3] - (4-methoxy) (2,6) pyridinophan (1 mmol) is dissolved in 15 ml of dry tetrahydrofuran. To this solution was added a solution of 270 mg of FeCl ₃ .6H ₂ O (1 mmol) in 5 ml of MeOH. The resulting mixture was evaporated to dryness and the solid was dissolved in 10 ml AcN with a minimum amount of MeOH. Slow diffusion of tetrahydrofuran gives 300 mg of brown crystals, yield 70%. Elemental analysis for C ₁₅ H ₁₈ N ₄ Cl ₃ OFe · 0.5 MeOH (found / theoretical): C 41.5 / 41.61; H 4.46 / 4.52; N 12.5 / 12.08.

IR (KBr granules, cm ^-1 ): 3545, 3414, 3235, 3075, 2883, 1615, 1477, 1437, 1340, 1157, 1049, 883, 628, 338.

Example 5

This example describes the synthesis of a catalyst of formula (H)

where R ₁ -R ₈ = H; x is 1; y = 1; z is 1; X = Cl, n = 2; Y = Cl ^- , p = 1.

Synthesis of the complex [Fe (LN ₄ H ₂ ) Cl ₂ ] Cl

240 mg of LN ₄ H ₂ (1 mmol) was dissolved in 15 ml of dry terahydrofuran. To this solution was added a solution of 270 mg of FeCl _{3 ·} 6H ₂ O (1 mmol) in 5 ml of MeOH. The resulting mixture was stirred to obtain directly 340 mg of a yellow powder, yield 85%.

IR (KBr granules, cm ^-1 ): 3445, 3031, 2851, 1629, 1062, 1473, 1427, 1335, 1157, 1118, 1045, 936, 796, 340, 318.

Example 6

This example describes the synthesis of a catalyst of formula (H)

where R ₁ = R ₂ = R _5-8 = H; R ₃ = R ₄ = Me; x is 1; y = 1; n is 2; z is 1; X = F ^- ; m is 2; Y = PF $\genfrac{}{}{0ex}{}{\text{-}}{\text{6}}$ ; p = 1.

Difluor [N, N'-dimethyl-2,11-diaza [3.3] (2.6) pyridinophan] manganese (III) hexafluorophosphate

2,6-Dichloromethylpyridine

(i) Synthesis of N, N’-dimethyl-1,11-diaz ligand [3.3] (2.6) pyridinophan

A mixture of 2,6-dimethanol-pyridine (5 g, 36 mmol) and 75 ml of SOCl ₂ was refluxed for 4 hours. The mixture was concentrated to half its volume and toluene (50 ml) was added. Then, the solid formed after cooling is filtered and dissolved in water, and the solution is neutralized with NaHCO ₃ . The resulting solid was filtered and dried (65%).

¹ H NMR (200 MHz, CDCl ₃ ): δ 7.8 (1H, t, J = 7 Hz), 7.45 (2H, d, J = 7 Hz), 4.7 (4H, s).

Sodium p-toluenesulfonamidur

To a mixture of Na ° in dry EtOH (0.7 g, 29 mmol) was added p-toluenesulfonamide (5 g, 29 mmol) and the solution was refluxed for 2 hours. After cooling, the resulting solid was filtered, washed with EtOH and dried (quantitative yield).

N, N’-Ditosyl-2,11-diaz [3.3] (2.6) pyridinophan

To a solution of sodium p-toluenesulfonamidur (1.93 g, 10 mmol) in 200 ml of dry dimethylformamide at 80 ° C, 2,6-dichloromethylpyridine (1.76 g, 10 mmol) was slowly added. After an hour, a new portion of p-toluenesulfonamidur (1.93 g) was added and the resulting mixture was stirred at 80 ° C. for another 4 hours. Then the solution is evaporated to dryness. The resulting solid was washed with water, then EtOH and finally crystallized in a mixture of CHCl ₃ / MeOH. The resulting solid was filtered and dried. The yield (15) is 55%.

¹ H NMR (200MHz, CDCl ₃ ): δ 7.78 (4H, d, J = 6Hz), 7.45 (6H, m), 7.15 (4H, d, J = 6Hz), 4.4 (8H, s), 2.4 (6H , s).

2,11-diaza [3.3] (2.6) pyridinophan

A mixture of N, N'-ditosyl-2,11-diaz [3.3] (2.6) pyridinophan (1.53 g, 2.8 mmol) and 14 ml of H ₂ SO ₄ , 90%, is heated at 110 ° C in within 2 hours. The solution, cooled and diluted with 14 ml of water, is then carefully poured into a saturated NaOH solution. The resulting solid was extracted with chloroform. The organic layer was evaporated to dryness to give 85% of 2.11-diaz [3.3] (2.6) pyridinophan.

¹ H NMR (200 MHz, CDCl ₃ ): δ 7.1 (2H, t, J = 7 Hz), 6.5 (4H, d, J = 7 Hz), 3.9 (8H, s).

N, N’-Dimethyl-2,11-diaz [3.3] (2.6) pyridinophan

A mixture of 2.11-diaz [3.3] (2.6) pyridinophan (0.57 g, 2.4 mmol), 120 ml of formic acid and 32 ml of formaldehyde (32% in water) was refluxed for 24 hours. Concentrated HCl (10 ml) was added and the solution was evaporated to dryness. The solid is dissolved in water, converted to base using 5 M NaOH and the resulting solution is extracted with CHCl ₃ . The resulting solid was purified by alox chromatography (CH ₂ Cl ₂ + 1% MeOH) to give 51% N, N'-dimethyl-2,11-diaz [3.3] (2.6) pyridinophan.

¹ H NMR (200 MHz, CDCl ₃ ): δ 7.15 (2H, t, J = 7 Hz), 6.8 (4H, d, J = 7 Hz), 3.9 (8H, s), 2.73 (6H, s).

(ii) Synthesis of the complex

MnF ₃ (41.8 mg, 373 mmol) was dissolved in 5 ml of MeOH and N, N'-dimethyl-2,11-diaza [3.3] (2.6) pyridinophan (0.1 g, 373 mmol) was added to the solution. with 5 ml of tetrahydrofuran. After 30 minutes of stirring at room temperature, 4 ml of tetrahydrofuran saturated in NBu ₄ PF _{6 was} added and the solution was left without stirring until crystallization was complete. The product was collected by filtration to obtain 80% of the complex.

Elementary analysis (found, theoretically),%:

C (38.35, 37.94), N (11.32, 11.1), H (3.75, 3.95).

IR (KBr granules, cm ^-1 ): 3086, 2965, 2930, 2821, 1607, 1478, 1444, 1425, 1174, 1034, 1019, 844, 796, 603, 574, 555.

UV-Vis (CH ₃ CN, λ, nm, ε): 500, 110; 850, 30; (CH ₃ CN / H ₂ O: 1/1, λ, nm, ε): 465, 168; 850, 30.

Example 7

Whitening stains of tomato oil on fabrics with and without [Fe (MeN4Py) (СН ₃ СN)] (ClO ₄ ) ₂ immediately after washing (t = 0) and after 24 hours (t = 1 day)

In a water solution containing 10 mM carbonate buffer (pH 10) without and with 0.6 g / L linear alkylbenzenesulfonate (LAS) or containing 10 mM borate buffer (pH 8) without and with 0.6 g / L LAS, wipes are immersed (6x6 cm) with spots of tomato soybean oil and stirred for 30 minutes at 30 ° C. In the second series of experiments, the same tests are carried out in the presence of 10 μM [Fe (MeN4Py) (CH ₃ CN)] (ClO ₄ ) ₂ , designated in the table below as Fe (MeN4Py).

After washing, the wipes are dried in a drum dryer and the reflection coefficient is measured using a 3700 Minolta spectrophotometer at 460 nm. The difference between the reflection coefficients before and after washing is designated as Δ R460.

The reflection coefficient of napkins is measured immediately after washing (t = 0) and 24 hours after they are in a dark room under ambient conditions (t = 1 day). The results are shown in table 1.

Thus, after processing tissue napkins, drying and storing them, a clear whitening effect is observed.

Example 8

Whitening stains of tomato oil on fabrics without and with the addition of various metal catalysts, measured 24 hours after they were in the dark under ambient conditions

In a water solution containing 10 mM carbonate buffer (pH 10) without and with 0.6 g / l of linear alkylbenzenesulfonate (LAS) or containing 10 mM borate buffer (pH 8) without and with 0.6 g / l of LAS, wipes are immersed with spots of tomato soybean oil, which are in this solution with stirring for 30 minutes at 30 ° C. In comparative experiments, the same tests are carried out by adding 5 μM dinuclear or 10 μM mononuclear complex shown in table 2.

After washing, the napkins are rinsed with water, then dried at 30 ° C, and after being in the dark for 24 hours, a Linotype-Hell scanner (formerly Linotype) measures color change. This change (including bleaching) is expressed as Δ E. The measured color difference (Δ E) between the washed and non-washed fabric is determined as follows:

Δ E = [(Δ L) ² + (Δ a) ² + (Δ b) ² ] ^1/2

where Δ L is a measure of the difference in darkness between the washed and non-washed test tissues; Δ a and Δ b are measures of differences in redness and yellowness between two tissues, respectively. This color measurement method is described by Commission International de l’Eclairage (CIE); Recommendation on Uniform Color Spaces, color difference equations, psychometric color terms, supplement no 2 to CIE Publication, no 15, Colormetry, Bureau Central de la CIE, Paris, 1978.

The following complexes are used.

i) [Mn ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (μ -O) ₃ ] - (PF ₆ ) ₂ (1),

synthesized in accordance with EP-B-458397;

ii) [Mn (LN4Me2)] (= difluoro [N, N’-dimethyl-2,11-diaza [3.3] (2,6) -pyridinophan] manganese (III) hexafluorophosphate) (2),

synthesized as previously indicated;

iii) [Fe (OMe) LN4H2) Cl ₂ ] (= Fe (2.11-diaza [3.3] - (4-methoxy) - (2.6) pyridinophan) Cl ₂ ) (3),

synthesized as previously indicated;

iv) Cl2-CoCo (4),

synthesized in accordance with EP-A-408131;

v) Me2CoCo (5),

synthesized in accordance with EP-A-408131;

vi) [Fe (tpen) (ClO ₄ ) ₂ (6),

synthesized in accordance with WO-A-9748787;

vii) [Fe (N, N, N'-Tris (pyridin-2ylmethyl) -N-methyl-1,2-ethylenediamine) Cl] (PF ₆ ) ₂ (7),

synthesized in accordance with I. Bernal et al., J. Chem. Soc., Dalton Trans, 22, 3667 (1995);

viii) [Fe ₂ (N, N, N'N'-tetrakis (benzimidazol-2-ylmethyl) propan-2-ol-1,3-diamine) (μ-OH) (NO ₃ ) ₂ ] NO ₃ ) ₂ (8),

synthesized in accordance with Brennam et al., Inorg. Chem., 30, 1957 (1991);

ix) [Mn ₂ (tpen) (μ-OAc] (ClO ₄ ) ₂ (9),

synthesized according to Toftlund N .; Markiewicz A .; Murray K.S., Acta Chem. Scamd., 44, 443 (1990);

x) [Mn (N, N'N'-tris (pyridin-2-ylmethyl) -N'-methyl-1,2-ethylenediamine) Cl] (PF ₆ ) (10).

Synthesized as follows.

To a solution of manganese tetrahydrate chloride in tetrahydrofuran (0.190 g, 1 mmol MnCl ₂ · 4H ₂ O in 10 ml of tetrahydrofuran) is added the trispicen ligand (NMe) to give a brown precipitate (ligand for comparison: I. Bemal et al., J. Chem. Soc., Dalton Trans, 22, 3667 (1995)). The mixture was stirred for 10 minutes and ammonium hexafluorophosphate (0.163 g, 1 mmol) dissolved in tetrahydrofuran was added to it to obtain a cream-colored precipitate. The mixture was filtered, the filtrate was washed with tetrahydrofuran and dried in vacuo to give the complex (total weight 522.21 g mol ^-1 ) as a white solid (0.499 g, 86%). ESMS (m / z): 437 ([LMnCl] ⁺ ).

xi) [Mn ₂ (N, N'-bis (pyridin-2-ylmethyl) -1,2-ethylenediamine) ₂ - (μ-O) ₂ ] (ClO ₄ ) ₃ (11),

synthesized in accordance with Glerup J .; Goodson P.A., Hazell R .; Hodgson D.J .; McKenzie C.J .; Michelsen K .; Rychlewska U .; Toftlund H. Inorg. Chem. (1994), 33 (18), 4105-11.

xii) [Mn (N, N'-bis (pyridin-2-ylmethyl) -N, N'-dimethyl-l, 2-ethylenediamine) ₂ Cl ₂ ] (12),

synthesized as follows.

Triethylamine (0.405 g, 1 mmol) is a solution of the bispicen ligand salt (NMe) (0.416 g, 1 mmol) in anhydrous tetrahydrofuran (10 ml) (ligand for comparison: C. Li et al., J. Chem. Soc., Dalton Trans. (1991), 1909-14). The mixture was stirred at room temperature for 30 minutes. A few drops of methanol are added. The mixture was filtered and manganese chloride (0.198 g, 1 mmol) dissolved in tetrahydrofuran (1 ml) was added thereto, yielding, after stirring for 30 minutes, a white precipitate. The solution was filtered, the filtrate was washed twice with dry ether and dried in vacuo to give 0.093 g of the complex (23% yield).

xiii) [Mn ₂ (N, N, N ', N'-tetrakis (pyridin-2-ylmethyl) propan-1,3-diamine) (μ-O) (μ-OAc) ₂ ] (ClO ₄ ) ₂ ( thirteen),

synthesized as follows.

To a stirred solution of 6.56 g of 2-chloromethylpyridine (40 mmol) and 0.75 ml of 1,3-propanediamine (9 mmol) in 40 ml of water, 8 ml of a 10 M NaOH solution are added slowly at 70 ° C for 10 minutes. . The color of the reaction changes from yellow to dark red. The solution was stirred for another 30 minutes at 70 ° C, after which it was cooled to room temperature. The reaction mixture was extracted with dichloromethane (200 ml in total), after which the red organic layer was dried over MgSO ₄ , filtered and evaporated under reduced pressure to obtain 4.51 g of a red-brown oil. After scraping the remainder from the bottom with a spool, it becomes hard; after trying to rinse the crude product with water, it becomes dirty, so the cleaning is immediately stopped and the product is dried with ether. For analysis of the product using NMR, a sample was taken, after which the residue was immediately reacted with Mn (OAc) ₃ (see complex formation).

¹ H NMR (400 MHz) (CDCl ₃ ), δ (ppm): 1.65 (q-5, propane-A, 2H), 2.40 (t, propane-B, 4H), 3.60 (s, N-CH ₂ - pir, 8H), 6.95 (t, pir-H4, 4H), 7.30 (d, pir-H3, 4H), 7.45 (t, pir-H5, 4H), 8.35 (d, pir-H6, 4H).

To a stirred solution of 4.51 g TPTN (0.0103 mol) in 40 ml of methanol at room temperature (22 ° C), 2.76 g of Mn (OAc) ₃ (0.0103 mol) was added. The color of the reaction changes from orange to dark brown; after addition, the mixture is stirred for 30 minutes at room temperature and filtered. 1.44 g of NaClO ₄ , (0.0103 mmol) was added to the filtrate at room temperature, and the reaction mixture was stirred for another hour, filtered and dried with nitrogen to give 0.73 g of bright brown crystals (8%).

¹ H NMR (400 MHz) (CD ₃ CN), δ (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 / (cm ^-1 ): 3426, 1608 (C = C), 1563 (C = N), 1487, 1430 (C-H), 1090 (ClO ₄ ), 1030, 767, 623.

UV / Vis (λ, nm (ε, l-mol ^-1 ): 260 (2.4 × 10 ⁴ ), 290 (sh), 370 (sh), 490 (5.1 × 10 ² ), 530 (sh; 3.4 × 10 ² ), 567 (sh), 715 (1.4 × 10 ² ).

Mass spectrum: (ESP +) m / z782 [TPTNMn (II) Mn (III) (μ-OH) (μ-ОАс) ₂ (СlO ₄ ) ^- ] ^+.

ESR (CH ₃ CN): the complex is not amenable to ESR, which confirms the presence of Mn (III) Mn (III).

Elemental analysis; found (expected for Mn ₂ С ₃₁ Н ₃₈ N ₆ O ₁₄ Сl ₂ (МW = 899): С 41.14 (41.4), Н 4.1 (4.2), N 9.23 (9.34), О 24.8 (24.9), Сl 7.72 (7.9 ), Mn 12.1 (12.2).

xiv) [Mn ₂ (tpa) ₂ (μ -O) ₂ ] (RF ₆ ) ₃ (14),

synthesized according to D.K. Towle, S.A. Botsford, D.J. Hodgson, ICA, 141, 167 (1988).

xv) [Fe (N4Py) (CH ₃ CN)] (ClO ₄ ) ₂ (15),

synthesized in accordance with WO-A-9534628.

xvi) [Fe (MeN4Py) (CH ₃ CN)] (ClO ₄ ) ₂ (16),

synthesized in accordance with EP-A-0909809.

xvii) [Mn ₂ (2,6-bis {(bis (2-pyridylmethyl) amino) methyl} -4-methylphenol)] - (μ -OAc) ₂ ] (ClO ₄ ) ₂ (17),

synthesized in accordance with H. Diril et al., J. Am. Chem. Soc., 111, 5102 (1989).

xviii) [Mn ₂ (N, N, N'N'-tetrakis (benzimidazol-2-ylmethyl) propan-2-olate-1,3-diamine)] (μ-OAc) ₂ ] (ClO ₄ ) ₂ (18 ),

synthesized in accordance with P. Marthur et al., J. Am. Chem. Soc., 109, 5227 (1987).

results

Table 2 shows the bleaching of stains from tomato oil, expressed in Δ E, obtained for various metal complexes, measured after 24 hours.

An experiment in an argon atmosphere (compound 16 at pH 10 with LAS) shows that there is no bleaching effect after storage, thus demonstrating the participation of oxygen in the bleaching process.

The following are the structures of the compounds used in the examples to illustrate various structures (metals and ligands) in accordance with the claims.

Example 1 as a Manganese Complex

[Mn ₂ (1,4,7-trimethyl] -1,4,7-triazacyclononane) ₂ (μ-O) ₃ ] (PF ₆ ) ₂ (1).

Example 2 as a Manganese Complex

[Mn (LN4Me2)] (= difluoro [N, N’-dimethyl-2,11-diaza [3.3] (2,6) pyridinophan] manganese (III) hexafluorophosphate) (2).

Example 3 as an iron complex

[Fe (OMeLN ₄ H ₂ ) Cl ₂ ] (= Fe [2,11-diaza [3.3] (4-methoxy) (2,6) pyridinophan) Cl ₂ (3).

Example 4 as a cobalt complex

Example 5 as a cobalt complex

Example 6 as an iron complex

[Fe (tetraphenylethylenediamine) (ClO ₄ ) ₂ (6).

Example 7 as an iron complex

[Fe (N, N, N'-Tris (pyridyl-2ylmethyl) -N-methyl-1,2-ethylenediamine) Cl] (PF ₆ ) ₂ (7).

Example 8 as an iron complex

[Fe ₂ (N, N, N ', N'-tetrakis (benzimidazol-2-ylmethyl) propan-2-ol-1,3-diamine) (μ-OH) (NO ₃ ) ₂ ] (NO ₃ ) ₂ (8).

Example 9 as a Manganese Complex

Example 10 as a Manganese Complex

Example 11 as a Manganese Complex

Example 12 as a Manganese Complex

Example 13 as a Manganese Complex

[Mn ₂ (N, N, N ', N'-tetrakis (pyridin-2-ylmethyl) propane-1,3-diamine) (μ-O) (μ-OAc) ₂ (ClO ₄ ) ₂ (13).

Example 14 as a Manganese Complex

[Mn ₂ (triphenylamine) ₂ (μ -O) ₂ ] (PF ₆ ) ₃ (14).

Example 15 as an iron complex

[Fe (N, N-bis (pyridin-2-yl) -1,1-bis (pyridin-2-yl) -1-aminoethane) (CH ₃ CN)] (ClO ₄ ) ₂ (15).

Example 16 as an iron complex

[Fe (methyl-N, N-bis (pyridin-2-yl) -1,1-bis (pyridin-2-yl) -1-aminoethane) (CH ₃ CN)] (ClO ₄ ) ₂ (16).

Example 17 as a Manganese Complex

[Mn ₂ (2,6-bis {(bis (2-pyridylmethyl) amino) methyl} -4-methylphenol)) (μ-OAc) ₂ ]) (ClO ₄ ) ₂ (17).

Example 18 as a Manganese Complex

[Mn (N, N, N'N'-tetrakis (benzimidazol-2-ylmethyl) propan-2-olate-1,3-diamine)] μ-OAc) ₂ (ClO ₄ ) ₂ (18).

Claims (63)

1. The method of processing a textile product by contacting it with an organic substance that forms a complex with a transition metal of the formula A1

in which M is a metal selected from Mn (II) - (III) - (IV) - (V), Cu (I) - (II) - (III), Fe (I) - (II) - (III) - (IV), Co (I) - (II) - (III), Ni (I) - (II) - (III), Cr (II) - (III) - (IV) - (V) - (VI ) - (VII), Ti (II) - (III) - (IV), V (II) - (III) - (IV) - (V), Mo (II) - (III) - (IV) - ( V) - (VI), W (IV) - (V) - (VI), Pd (II), Ru (II) - (III) - (IV) - (V) and Ag (I) - (II) ; L is a ligand of the general formula (BI)

where g = 0 or an integer from 1 to 6; r is an integer from 1 to 6; s = 0 or an integer from 1 to 6; Z1 and Z2 independently from each other represent a heteroatom or a heterocyclic or heteroaromatic ring, while Z1 and / or Z2 may be substituted by one or more functional groups E, as described below; Q1 and Q2 independently from each other represent a group of the formula:

where 10> d + e + f> 1; d is 0-9; e = 0-9; f is 0-9; each Y1 is independently selected from —O—, —S—, —SO—, —SO ₂ -, - (G ¹ ) N—, - (G ¹ ) (G ² ) N- (where G ¹ and G ² are as follows), —C (O) -, arylene, alkylene, heteroarylene, —P— and —P (O) -; if s> 1, then each - [Z1 (R1) - (Q1) _r -] - group is independently defined; R1-R9 are independently selected from —H, hydroxy-C ₀ -C ₂₀ -alkyl, halogen-C ₀ -C ₂₀ -alkyl, nitroso, formyl-C ₀ -C ₂₀ -alkyl, carboxyl-C ₀ -C ₂₀ -alkyl as well as their esters and salts, carbamoyl-C ₀ -C ₂₀ -alkyl, sulfo-C ₀ -C ₂₀ -alkyl, as well as their esters and salts, sulfamoyl-C ₀ -C ₂₀ -alkyl, amino-C ₀ -C ₂₀ -alkyl, aryl-C ₀ -C ₂₀ -alkyl, heteroaryl-C ₀ -C ₂₀ -alkyl, C ₀ -C ₂₀ -alkyl, alkoxy-C ₀ -C ₈ -alkyl, carbonyl-C ₀ - C ₆ alkoxy, aryl-C ₀ -C ₆ alkyl and C ₀ -C ₂₀ alkylamide; E is selected from functional groups containing oxygen, sulfur, phosphorus, nitrogen, selenium, halogens, as well as any electron donor and / or acceptor groups, E is preferably selected from hydroxy, mono- or polycarboxylate derivatives, aryl, heteroaryl, sulfonate, thiol (- RSH), thioethers (-RS-R '), disulfides (-RSSR'), dithiolenes, mono- or polyphosphonates, mono- or polyphosphates, electron-donating and electron-withdrawing groups, as well as groups of formulas (G ¹ ) (G ² ) N- , (G ¹ ) (G ² ) (G ³ ) N-, (G ¹ ) (G ² ) NC (O) -, G ³ O- and G ³ C (O) -, where each of G ¹ , G ² and G ³ are independently selected from vodor Yes, alkyl, electron-donating and electron-withdrawing groups, in addition to any amongst the foregoing groups; or one of R1-R9 represents a bridging group —C _{n ′} (R11) (R12) - (D) _p —C _{m ′} (R11) (R12) - linked to another residue of the same general formula, where p = 0 or 1, D is selected from a heteroatom or 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, provided that each of n '+ m '<= 4, R11 and R12 are independently independently selected from —H, NR13 and OR14, alkyl, aryl optionally substituted, and each of R13 and R14 are independently selected from —H, and lkila, aryl, both of which are possibly substituted; T1 and T2 independently of each other are groups R4 and R5, where R4 and R5 have the meanings given for R1-R9, and if g = 0, as> 0, then R1 together with R4 and / or R2, together with R5 may independently represent = CH-R10, where R10 is as defined for R1-R9, or T1 and T2 together (-T2-T1-) can be a covalent bond when s> 1 and g> 0; if Z1 and / or Z2 represent N, T1 and T2 together represent a single bond, and R1 and / or R2 are absent, then 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 are independently linked together by a covalent bond; if Z1 and / or Z2 is O, then R1 and / or R2 do not exist; if Z1 and / or Z2 is S, N, P, B or Si, then R1 and / or R2 may be absent; if Z1 and / or Z2 is a heteroatom substituted by a functional group E, then R1 and / or R2 and / or R4 and / or R5 may be absent, X is a coordinating group selected from any mono-, bi- or tri-charged anions and any neutral molecules capable of coordinating the metal in a mono-, bi- or tridentate way; Y is any uncoordinated counterion; a is an integer from 1 to 10; k is an integer from 1 to 10; n = 0 or an integer from 1 to 10; m = 0 or an integer from 1 to 20. in the absence of hydrogen peroxide or the whitening system forming it, wherein said complex catalyzes the bleaching of a dry textile product with atmospheric oxygen after treatment with said complex and drying. 2. The method according to claim 1, in which T1 and T2 independently from each other represent groups R4 and R5 having the meanings indicated for R1-R9, in accordance with the general formula (BIII)

3. The method according to claim 2, in which in the General formula (BIII) s = 1; r is 1; g is 0; d = f = 1; e is 1-4; Y1 = —CH ₂ -; and R1 together with R4 and / or R2 together with R5 independently of each other are = CH-R10, where R10 has the meanings indicated for R1-R9. 4. The method according to claim 3, in which R2 together with R5 represents = CH-R10. 5. The method according to claim 3 or 4, in which the ligand is selected from

6. The method according to claim 5, in which the ligand is selected from

where R1 and R2 are selected from optionally substituted phenols, heteroaryl-C ₀ -C ₂₀ alkyl; R3 and R4 are selected from —H, alkyl, aryl, optionally substituted phenols, heteroaryl-C ₀ -C ₂₀ -alkyls, alkylaryl, aminoalkyl, alkoxy. 7. The method according to claim 6, in which R1 and R2 are selected from optionally substituted phenols, heteroaryl-C ₀ -C ₂ -alkyls, R3 and R4 are selected from -H, alkyl, aryl, optionally substituted phenols, nitrogen-heteroaryl-C ₀ - C ₂ -alkyl. 8. The method according to claim 7, in which in the complex [M _a L _k X _n ] Y _m M - Mn (II) - (IV), Co (II) - (III), Fe (II) - (III) ; X - CH ₃ CN, OH ₂ , Cl ^- , Br ^- , OCN ^- , N $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , SCN ^- , OH ^- , O ^2- , PO $\genfrac{}{}{0ex}{}{\text{3-}}{\text{4}}$ , C ₆ H ₅ BO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{2}}$ , RCOO ^- ; Y - ClO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ BPh $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , Br ^- , Cl ^- , [FeCl ₄ ] ^- , PF $\genfrac{}{}{0ex}{}{\text{-}}{\text{6}}$ , NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ ; a = 1, 2, 3,4; n is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9; m is 1, 2, 3, 4; k = 1, 2, 4. 9. The method according to claim 8, in which in the General formula (BIII) s = 1; r is 1; g is 0; d = f = 1; e is 1-4; Y1 = -C (R ’) (R’ ’), where R’ and R ’’ independently have the meanings indicated for R1-R9. 10. The method according to claim 9, in which the ligand has the General formula

11. The method according to claim 10, in which R1, R2, R3, R4, R5 are —H or C ₀ –C ₂₀ alkyl, n = 0 or 1, R6 is —H, alkyl, —OH or - SH, a R7, R8, R9, R10 are each independently selected from —H, C ₀ -C ₂₀ -alkyl, heteroaryl-C ₀ -C ₂₀ -alkyl, alkoxy-C ₀ -C ₈ -alkyl and amino C ₀ -C ₂₀ alkyl. 12. The method according to claim 11, in which in the complex [M _a L _k X _n ] Y _m M - Mn (II) - (IV), Fe (II) - (III), Cu (I), Co (II ) - (III); X - CH ₃ CN, OH ₂ , Cl ^- , Br ^- , OCN ^- , N $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , SCN ^- , OH ^- , O ^2- , PO $\genfrac{}{}{0ex}{}{\text{3-}}{\text{4}}$ , C ₆ H ₅ BO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{2}}$ , RCOO ^- ; Y - ClO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , BPh $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , Br ^- , Cl ^- , [FeCl ₄ ] ^- , PF $\genfrac{}{}{0ex}{}{\text{-}}{\text{6}}$ NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ ; a = 1, 2, 3, 4; n is 0, 1, 2, 3, 4; m is 0, 1, 2, 3, 4, 5, 6, 7, 8; k = 1, 2, 3, 4. 13. The method according to item 12, in which in the General formula (BIII) s = 0; g is 1; d = e = 0; f = 1 - 4. 14. The method according to item 13, in which the ligand has the General formula

15. The method according to 14 provided that none of R1-R3 is hydrogen. 16. The method according to 14 or 15, in which the ligand has the General formula

where R1, R2, R3 have the meanings indicated for R2, R4, R5. 17. The method according to any one of claims 13-16, wherein in the complex [M _a L _k X _n ] Y _m M - Mn (II) - (IV), Fe (II) - (III), Cu (II) , Co (II) - (III); X - CH ₃ CN, OH ₂ , Cl ^- , Br ^- , OCN ^- , N $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , SCN ^- , OH ^- , O ^2- , PO $\genfrac{}{}{0ex}{}{\text{3-}}{\text{4}}$ , C ₆ H ₅ BO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{2}}$ , RCOO ^- ; Y - ClO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ BPh $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , Br ^- , Cl ^- , [FeCl ₄ ] ^- , PF $\genfrac{}{}{0ex}{}{\text{-}}{\text{6}}$ , NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ ; a = 1, 2, 3, 4; n is 0, 1, 2, 3, 4; m = 0, 1, 2, 3, 4, 5, 6, 7, 8 and k = 1, 2, 3, 4. 18. The method according to claim 1, where Z1 and Z2 independently from each other are an optionally substituted heteroatom selected from N, P, O, S, B and Si or an optionally substituted heterocyclic or heteroaromatic ring selected from pyridine, pyrimidines, pyrazine , pyramidine, pyrazole, pyrrole, imidazole, benzimidazole, quinolein, isoquinoline, carbazole, indole, isoindole, furan, thiophene, oxazole and thiazole. 19. The method according to claim 1 or 18, in which T1 and T2 together form a simple bond, a s> 1, in accordance with the general formula (BII):

where Z3 independently represents a group having the meanings indicated for Z1 or Z2; R3 independently represents a group having the meanings given for R1-R9; Q3 independently represents a group having the meanings indicated for Q1, Q2; h = 0 or an integer from 1 to 6; s ’= s-1. 20. The method according to claim 19, in which in the General formula (BII) s ’= 1, 2 or 3; r = g = h = 1; d is 2 or 3; e = f = 0; R6 = R7 = H. 21. The method according to claim 20, in which the ligand L has a General formula selected from

22. The method according to item 21, in which the ligand has a General formula selected from

23. The method according to item 22, in which R1, R2, R3 and R4 are independently selected from —H, alkyl, heteroaryl or represent a bridging group linked to another residue of the same general formula, wherein the bridging group is alkylene, or oxyalkylene, or heteroaryl-containing bridge. 24. The method according to item 23, in which R1, R2, R3 and R4 are independently selected from —H, methyl, ethyl, isopropyl, a nitrogen-containing heteroaryl, or a bridging group bonded to another residue of the same general formula, wherein the bridging the group is alkylene or hydroxyalkylene. 25. The method according to any one of claims 20-24, wherein the complex [M _a L _k X _n ] Y _m M is Mn (II) - (IV), Cu (I) - (III), Fe (II) - (III), Co (II) - (III); X - CH ₃ CN, OH ₂ , Cl ^- , Br ^- , OCN ^- , N $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , SCN ^- , OH ^- , O ^2- , PO $\genfrac{}{}{0ex}{}{\text{3-}}{\text{4}}$ , C ₆ H ₅ VO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{2}}$ , RCOO ^- ; Y - ClO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ BPh $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , Br ^- , Cl ^- , [FeCl ₄ ] ^- , PF $\genfrac{}{}{0ex}{}{\text{-}}{\text{6}}$ NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ ; a = 1, 2, 3, 4; n is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9; m = 1, 2, 3, 4 and k = 1, 2, 4. 26. The method according to claim 19, in which in the General formula (BII) s ’= 2; r = g = h = 1; d = f = 0; e = 1, and each of Y1 is independently alkylene or heteroarylene. 27. The method according A.25, in which the ligand has the General formula

where A ₁ , A ₂ , A ₃ , A _{4 are} independently selected from C _1-9 alkylene or heteroarylen groups; N ₁ and n ₂ independently from each other represent a heteroatom or heteroarylene group. 28. The method according to item 27, in which N ₁ represents aliphatic nitrogen; N ₂ represents a heteroarylene group; R1, R2, R3, R4 each independently represents —H, alkyl, aryl or heteroaryl; and A ₁ , A ₂ , A ₃ , A ₄ each represents —CH ₂ -. 29. The method according to p, in which the ligand has the General formula

where each of R1 and R2 independently of one another is —H, alkyl, aryl or heteroaryl. 30. The method according to any one of claims 26-29, wherein in the complex [M _a L _k X _n ] Y _m M - Fe (II) - (III), Mn (II) - (IV), Cu (II) , Co (II) - (III); X - CH ₃ CN, OH ₂ , Cl ^- , Br ^- , OCN ^- , N $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , SCN ^- , OH ^- , O ^2- , PO $\genfrac{}{}{0ex}{}{\text{3-}}{\text{4}}$ , C ₆ H ₅ BO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{2}}$ , RCOO ^- ; Y - ClO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ BPh $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , Br ^- , Cl ^- , [FeCl ₄ ] ^- , PF $\genfrac{}{}{0ex}{}{\text{-}}{\text{6}}$ NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ ; a = 1, 2, 3, 4; n is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9; m = 1, 2, 3, 4 and k = 1, 2, 4. 31. The method according to claim 19, in which in the general formula (BII) s ’= 2, a r = g = h = 1 in accordance with the general formula

32. The method according to p, in which Z1 = Z2 = Z3 = Z4 - heteroaromatic ring; e = f = 0; d = 1, and R7 is absent. 33. The method according to p, in which each of Z1-Z4 represents N; R1-R4 are absent; both Q1 and Q3 are = CH - [- Y1-] _e -CH =, and both Q2 and Q4 are -CH ₂ - [- Y1-] _n -CH ₂ -. 34. The method according to p, in which the ligand L has the General formula

where A represents an optionally substituted alkylene, optionally interrupted by a heteroatom, and n = 0 or an integer from 1 to 5. 35. The method according to clause 34, wherein R1-R6 are hydrogen, n = 1, and A is —CH ₂ -, —CHOH—, —CH ₂ N (R) CH ₂ - or CH ₂ CH ₂ N ( R) CH ₂ CH ₂ -, where R represents hydrogen or alkyl. 36. The method according to clause 34, wherein A is —CH ₂ -, —CHHO— or —CH ₂ CH ₂ NHCH ₂ CH ₂ -. 37. The method according to any one of claims 31-36, wherein in the complex [M _a L _k X _n ] Y _m M - Mn (II) - (IV), Co (II) - (III), Fe (II) - (III); X - CH ₃ CN, OH ₂ , Cl ^- , Br ^- , OCN ^- , N $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , SCN ^- , OH ^- , O ^2- , PO $\genfrac{}{}{0ex}{}{\text{3-}}{\text{4}}$ , C ₆ H ₅ BO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{2}}$ , RCOO ^- ; Y - ClO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ BPh $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , Br ^- , Cl ^- , [FeCl ₄ ] ^- , PF $\genfrac{}{}{0ex}{}{\text{-}}{\text{6}}$ NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ ; a = 1, 2, 3, 4; n is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9; m = 1, 2, 3, 4 and k = 1, 2, 4. 38. The method according to claim 1, in which L is a pentadentate ligand of the General formula (B)

where each of R ¹ , R ² independently from each other represents-R ⁴ -R ⁵ ; R ³ represents hydrogen, optionally substituted by alkyl, aryl or arylalkyl, or —R ⁴ —R ⁵ , each of R ⁴ independently is a single bond or an optionally substituted alkylene, alkenylene, hydroxyalkylene, aminoalkylene, alkylene ether, carboxylic acid ester or amide; each of R ⁵ 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. 39. The method according to § 38, provided that R ^{3 is} not hydrogen. 40. The method according to claim 1, in which L is a pentadent or hexadentate ligand of the General formula (C) R ¹ R ¹ NW-NR ¹ R ² , where each of R ¹ independently is —R ³ -V, where R ³ is an optionally substituted alkylene, alkenylene, hydroxyalkylene, aminoalkylene or alkylene ether, and V is an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl; W is an optionally substituted alkylene bridging group selected from —CH ₂ CH ₂ -, —CH ₂ CH ₂ CH ₂ -, —CH ₂ CH ₂ CH ₂ CH ₂ -, —CH ₂ —C ₆ H ₄ —CH ₂ - , —CH ₂ —C ₆ H ₁₀ —CH ₂ - and —CH ₂ —C ₁₀ H ₆ —CH ₂ -; R ² represents a group selected from R ¹ , as well as alkyl, aryl and aralkyl groups optionally substituted with a substituent selected from oxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic acid ester, sulfonate, amine, alkylamine and N ⁺ (R ⁴ ) ₃ , where R ^{4 is} selected from hydrogen, alkanyl, alkenyl, arylalkanyl, arylalkenyl, hydroxyalkanyl, hydroxyalkenyl, aminoalkanyl, aminoalkenyl, alkanyl ether and alkenyl ether. 41. The method according to claim 1, in which L is a macrocyclic ligand of the formula (E)

where Z ¹ and Z ^{2 are} independently selected from monocyclic or polycyclic aromatic ring structures optionally containing one or more heteroatoms, with each aromatic ring structure being substituted with one or more substituents; Y ¹ and Y ^{2 are} independently selected from atoms C, N, O, Si, P and S; A ¹ and A ^{2 are} independently selected from hydrogen, alkyl, alkenyl, and cycloalkyl, each of alkyl, alkenyl, and cycloalkyl being optionally substituted with one or more groups selected from hydroxy, aryl, heteroaryl, sulfonate, phosphate, electron-releasing, and electron-removing groups, as well as groups of formulas (G ¹ ) (G ² ) N-, G ³ OC (O) -, G ³ O- and G ³ C (O) -, where each of G ¹ , G ² and G ^{3 is} independently from each other selected from hydrogen and alkyl, as well as electron-giving and / or removing groups (in addition to the groups contained in the above compounds); i and j are selected from 0, 1 and 2, completing the valency of the groups Y ¹ and Y ² ; each of Q ¹ -Q ^{4 are} independently selected from groups of the formula

where 10> a + b + c + d> 2; each of Y ^{3 is} independently selected from —O—, —S—, —SO—, —SO ₂ -, - (G ¹ ) (G ² ) N—, - (G ¹ ) N-, (where G ¹ and G ² have the above meanings), -C (O) -, aryl, heteroaryl, -P- and -P (O) -; each of A ³ -A ^{6 is} independently selected from groups having the above values for A ¹ and A ² , and where any two or more of A ¹ -A ⁶ together form a bridging group, provided that if A ¹ and A ² linked without simultaneous binding to any of A ³ -A ⁶ , the bridging group linking A ¹ and A ² must contain at least one carbonyl group. 42. The method according to claim 1, in which in the formula (A1). X is a coordinating group selected from O ^2- , RBO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{2}}$ , RCOO ^- , RCONR ^- , OH ^- , NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{2}}$ , NO, CO, S ^2- , RS ^- , РО $\genfrac{}{}{0ex}{}{\text{4-}}{\text{3}}$ derivatives of sodium tripolyphosphate anions, PO ₃ OR ^3- , Н ₂ O, СО $\genfrac{}{}{0ex}{}{\text{2-}}{\text{3}}$ NSO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , ROH, NRR'R ", RCN, Cl ^- , Br ^- , OCN ^- , SCN ^- , CN ^- , N $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , F ^- , I ^- , RO ^- , ClO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ SO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{4}}$ HSO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ SO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{3}}$ and RSO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ ; and Y is a counterion selected from ClO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , BR $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , [FeCl ₄ ] ^- , PF $\genfrac{}{}{0ex}{}{\text{-}}{\text{6}}$ , RCOO ^- , NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{2}}$ , RO ^- , N ⁺ RR'R``R ''', Cl <sup>-</sup> , Br <sup>-</sup> , F <sup>-</sup> , I <sup>-</sup> , RSО $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , S <sub>2</sub> O $\genfrac{}{}{0ex}{}{\text{2-}}{\text{6}}$ , OCN <sup>-</sup> , SCN <sup>-</sup> , Li <sup>+</sup> , Ba <sup>2+</sup> , Na <sup>+</sup> , Mg <sup>2+</sup> , K <sup>+</sup> , Ca <sup>2+</sup> , Cs <sup>+</sup> , PR $\genfrac{}{}{0ex}{}{\text{+}}{\text{4}}$ RBO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{2}}$ SO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{4}}$ HSO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , SO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{3}}$ , SbСl $\genfrac{}{}{0ex}{}{\text{-}}{\text{6}}$ CuCl $\genfrac{}{}{0ex}{}{\text{2-}}{\text{4}}$ , CN, PO $\genfrac{}{}{0ex}{}{\text{3-}}{\text{4}}$ HPO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{4}}$ , H <sub>2</sub> PO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ derivatives of sodium tripolyphosphate anions, СО $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ F <sup>2-</sup> , NSO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ and bf $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ where R, R ′, R ″, R ″ ″ independently represent a group selected from hydrogen, hydroxyl, -OR (where R is alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or carbonyl derivative group), -OAr, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and carbonyl derivatives, each of R, Ar, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and carbonyl derivatives is optionally substituted with one or more functional groups R6 together with R7 and independently R8 together with R9 are oxygen; E is selected from functional groups containing oxygen, sulfur, phosphorus, nitrogen, selenium, halogens, as well as any electron-donating and / or electron-withdrawing groups. 43. The method according to § 42, in which in the formula (A1) M is a metal selected from Mn (II) - (III) - (IV) - (V), Cu (I) - (II), Fe (II) - (III) - (IV) and Co (I) - (Ii) to (iii); X is a coordinating group selected from O <sup>2-</sup> , RBO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{2}}$ , RCOO <sup>-</sup> , OH <sup>-</sup> , NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{2}}$ , NO, CO, CN <sup>-</sup> , S <sup>2-</sup> , RS <sup>-</sup> , РО $\genfrac{}{}{0ex}{}{\text{4-}}{\text{3}}$ , H <sub>2</sub> O, WITH $\genfrac{}{}{0ex}{}{\text{2-}}{\text{3}}$ NSO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , ROH, NRR'R '', Cl <sup>-</sup> , Br <sup>-</sup> , OCN <sup>-</sup> , SCN <sup>-</sup> , RCN, N $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , F <sup>-</sup> , I <sup>-</sup> , RO <sup>-</sup> , ClO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ SO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{4}}$ HSO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ SO <sub>2</sub> and RSO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ ; Y is a counterion selected from ClO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , BR $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , [FeCl <sub>4</sub> ] <sup>-</sup> , PF $\genfrac{}{}{0ex}{}{\text{-}}{\text{6}}$ , RCOO <sup>-</sup> , NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ NO $\genfrac{}{}{0ex}{}{\text{-}}{\text{2}}$ , RO <sup>-</sup> , N <sup>+</sup> RR'R``R ''', Cl ^- , Br ^- , F ^- , I ^- , RSО $\genfrac{}{}{0ex}{}{\text{-}}{\text{3}}$ , S ₂ O $\genfrac{}{}{0ex}{}{\text{2-}}{\text{6}}$ , OCN ^- , SCN ^- , Li ⁺ , Ba ²⁺ , Na ⁺ , Mg ²⁺ , K ⁺ , Ca ²⁺ , PR $\genfrac{}{}{0ex}{}{\text{+}}{\text{4}}$ SO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{4}}$ HSO $\genfrac{}{}{0ex}{}{\text{-}}{\text{4}}$ , SO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{3}}$ and BF _4— wherein R, R ′, R ″, R ″ ″ are hydrogen, optionally substituted alkyl or aryl; a is an integer from 1 to 4; k is an integer from 1 to 10; n = 0 or an integer from 1 to 4, and m = 0 or an integer from 1 to 8. 44. The method according to any one of claims 1 to 43, in which the processing includes contacting the textile product with organic matter in dry form. 45. The method according to any one of claims 1 to 44, in which the processing includes contacting the textile product with a solution containing organic matter, and then drying. 46. The method according to item 45, in which the solution is an aqueous solution. 47. The method according to item 46, in which the solution is a liquid for processing tissue by spraying. 48. The method according to clause 47, in which the solution is a washing solution for cleaning using washing. 49. The method according to item 45, in which the solution is an anhydrous solution. 50. The method according to 49, in which the solution is a liquid for dry cleaning. 51. The method according to 49, in which the solution is an aerosol spray liquid. 52. The method according to item 45, in which the medium has a pH value of from 6 to 11. 53. The method according to paragraph 52, in which the solution has a pH from 8 to 10. 54. The method according to any one of claims 45-53, wherein the solution is substantially devoid of a transition metal sequestrant. 55. The method according to any one of claims 45-54, wherein the solution also includes a surfactant. 56. The method according to any one of claims 45-54, wherein the solution also comprises a detergent component. 57. The method according to any one of claims 1 to 56, in which the organic substance comprises a preformed complex of a ligand and a transition metal. 58. The method according to any one of claims 45-56, wherein the organic substance comprises a free ligand complexed with a transition metal present in the solution. 59. The method according to any one of claims 1 to 56, in which the organic substance includes a free ligand, forming a complex with a transition metal present in a textile product. 60. The method according to any one of claims 1 to 56, in which the organic substance comprises a composition of a free ligand or a complex of a metal ligand substituted by a transition metal, and a source of a transition metal. Priority on points: 04/01/1999 PP 1-27, 29, 30-39, 43-59; 09/01/1998 according to paragraphs 28 and 29; 03/19/1999 according to pp.40-42.