COMPLEX COMPOUNDS CONTAINING SULFONATED PHENYL PHOSPHANES

02-06-1990 дата публикации
Номер:
CA0002004441A1
Принадлежит: Hoechst AG
Контакты:
Номер заявки: 2004441
Дата заявки: 01-12-1989

[1]

s V 2004441 COMPLEX COMPOUNDS CONTAINING SULFONATED PHENYL PHOSPHANES The invention relates to a new complex compounds of elements of the Groups IB, VIIA , AND VIIIÀ of the Periodic Table [IUPAC Version]. The common feature of these compound is that they contain the trisodium salt of tris(m-sulfo- phenyDphosphane as the complex ligand and optionally other ligands. The compounds are soluble in water without decomposition. Background of the Invention Complex compounds which contain the trisodium salt of m-trisulfonated triphenylphosphane of the chemical formula P(C6Hrni-S03Na)3 as the only ligand or as one of several ligands, are littl€. known. DE 27 00 90A C2,published July 14, 1977 Example 12, describes thereaction of bis (l,5-cyclooctadiene)nickel with the trisodium salt of tris- (m-sulfophenyl)phosphane (hereinafter TPPTS). A red compound is obtained which is recovered as a solid substance from its aqueous solution by evaporation in a vacuum. The Inventors claim that this compound is the tetrakis-tri-sodium salt of tris[m*-sulfophenyl)- phosphanelnickel(O). In the same publication, there is also general information on the preparation of TPPTS complex compounds of iron and palladium. Water-soluble compounds, or those compounds which dissolve under the reaction conditions, are reacted with aqueous TPPTS solution in the presence of a reducing agent, e.g. Na[BH4], K[BH4], zinc powder, magnesium, or boron hydrides. Neither the preparation process nor the individual compounds are described in further detail through examples or even characterized. _ 2004.441 Complex compounds containing TPPTS as a ligand, without the exact composition of these compounds being known, are formed from metal or metal compounds, TPPTS and optionally other ligands in various reactions. Thus, rhodium complexes with TPPTS ligands have recently gained special significance as components of catalyst systems which are used in the hydroformylation of olefins. Compared with other catalysts which are used for the same reaction, they have the advantage of being soluble in water. Therefore, the hydroformylation can be performed in a heterogeneous reaction medium consisting of aqueous and organic phases (two-phase system), with the result that the reaction product can then be separated from the water-soluble catalyst by simple phase separation. Furthermore, this procedure ensures that the valuable noble metal catalyst can be recovered with almost no loss, or recycled to the synthesis stage. Such a process is described, for example, in the DE 26 27 354 B2, published December 23, 1976. The addition of hydrogen cyanide to unsaturated organic compounds can also be performed in the presence of a compound of zero-valent nickel or iron or palladium of reduced valency and an aqueous solution of a sulfonated triphenylphosphane, in particular an aqueous solution of TPPTS, as a catalyst. This procedure is described in the DE 27 00 904 C2 previously cited. Instead of the nickel salt and TPPTS solution, a specially prepared complex compound, to which the composition Ni(TPPTS)4 is ascribed, can also be used as the catalyst. In spite of the afore-mentioned advantages of using water-soluble TPPTS complex compounds as catalysts, nothing is known about their use in other reactions. This situation is probably largely due to the fact that, despite intensive efforts, it has so far not been possible to isolate TPPTS-containing, water-soluble complex compounds in pure form and thus to permit their substance characterization by chemical and physical analytical processes. The problem to be solved by the present invention was, therefore, to prepare TPPTS'-containing complex compounds of certain metals, said compounds having a definite reproducible composition. Summary of the Present Invention i The invention consists in new complex compounds of the elements of the Groups IB, VIIA, and VIIIA of the Periodic Table, with the exception of the reaction product of bis(l,5«-cyclooctadiene)nitkel with the trisodium salt of tris(flif-sulf©phenyl)phosphane. The compounds are characterized in that they contain the trisodium salt of trisdn-sulfophenyDphosphane as the complex ligand and optionally other ligands. Detailed Description of the Invention The new compounds can be represented by the general formula. LyLMY(TPPTS)2 In this formula, L and L denote the same or different ligands, which, in additiort to TPPTS, can be bound to the central atom in the complex compound. Typical ligands are CO, NO, PFj, H20, S, halogen, such as Cl,y "aromatic ligands such as cyclopentadienyl, 1 -olefin ligands, such as cyclooctadiene, and /-acetylene ligands such as diphenylacetylene. M stands for the elements of the groups Ib, VIIA, and VIIIA of the Periodic Table as the central atom, in particular, manganese, iron, nickel, palladium, platinum, copper, silver or gold; w, x, y and z are integers, w and x each denoting 0 to 7y, y being 1 to 6 and z being = 4y. The new compounds are crystalline./ mostly coloured . substances. They are soluble in water without decompos¬ ition and can be isolated from the aqueous solution as hydrates in the form of powders or crystals. These hydrates contain one molecule of water per sodium ion. At room temperature the majority are stable in air. The claimed compounds can be prepared via various routes: - by synthesis from simple compounds/ i.e. salts of the element which forms the central atom of the complex compound ; - by ligand exchange reaction from complex compounds according to LiL2x+zMy + z TPPTS >I';iI'*My(TI>PTS)z + Zl2 where L r L and Mas well as xr y and z have the afore-mentioned meanings with the proviso that z is 2o smaller than or equal to x? - by introduction of TPPTS ligands into complex com¬ pounds/ said introduction not taking place by simple ligand exchange in the sense of the afore-mentioned equation but by elimination and/or substitution reactions. For synthesis from simple compounds it is expedient to proceed from water-soluble salts. The type of anion generally has no influence on the course of the react- ,4- s.. ion. For example/ the halidesr in particular the chlor¬ ides/ salts of oxygen acids such as nitrates and sul¬ fates, as well as salts of carboxylic acids such as formates and acetates, are all suitable. The salt dis¬ solved in water is reacted with aq, aqueous TPPTS solu¬ tion in stoichiometric ratio or in excess. If the oxidation stage of the metal in the complex compound is lower than in the starting saltf either excess TPPTS can act as a reducing agents or a reducing agent can be added to the reaction solution. Suitable reducing agents arer for example/ NatBHK or hydrazine hydrate. In this case it is recommended to conduct the reaction under the exclusion of air as well. In general/ the reaction readily takes place at room temperature; only seldom must it be accelerated or completed by increas¬ ing the temperature. When the claimed compounds are prepared by ligand exchange/ complex compounds of the respective metals are used as starting substances. Depending on their solubility/ they are dissolved in water or in an or¬ ganic solvent such as aromatic hydrocarbons (e.g. toluene)/ halogenated hydrocarbons (e.g. chloroform)/ alcohols (e.g. ethanol) or heterocyclic compounds (e.g. tetrahydrofuran). TPPTS is again used in the form of an aqueous solution and added in stoichiometric ratio or in excess. With synthesis by ligand exchange it is also sufficient to work at room temperature. Even if the starting complex compound is dissolved in an organic solvent immiscible in water/ which means that the reaction takes place in a liquid two-phase system/ short react¬ ion times are sufficient; intensive stirring promotes the reaction. The preparation of the new complex compounds by elimin¬ ation and substitution reactions takes place in a similar manner and under conditions comparable with those of the synthesis by ligand exchange. Other li- gands are introduced into the complex compounds in the known mannerf e.g. by feeding in CO or by adding a compound which splits off the nitrosyl radical, a sulfur or hydride group. In order to work up the reaction product and isolate th6 new compounds which are present in aqueous solu¬ tion regardless of the preparation process used/ the water is evaporated in a vacuunw optionally after previous filtration of the solution. In general Lhic, route does not lead to pure compounds but contaminated products or also mixtures of various TPPTS complex compounds which have formed concurrently during prepar¬ ation. It is therefore necessary to use special purifi¬ cation and separating processes to recover the pure substances. Gel chromatography, which is the subject of the German patent DE 38 22 036 Al has proved particularly suitable for solving this task. With this technique attention must also be paid to the exclusion of light or air depending on the properties of the compound in question; the eluent and the elution rate also depend on the particular purification or separ¬ ation problem in question. After this treatment the compounds are analytically and spectroscopically pure. As previously mentioned, the new compounds crystallize out of the aqueous solution as hydrates. The anhydrous compounds can be prepared from them without any decom¬ position occurring by means of water extraction under mild conditions, i.e. at temperatures below the melt or decomposition point and using reduced pressure, preferably a high vacuum. Therefore, the present invention includes both the water-containing and the water-free TPPTS complexes. The compounds according to the invention are catalytic- ally active and are successfully used as catalysts or components of catalysts in various reactions. Special mention should be made of the fact that the use of pure compounds prevents side and secondary reactions IQ which reduce the yield and often occur when the cat¬ alyst is formed in the reaction mixture "in situ". This situation is due to the fact that the "in situ prepar¬ ation" is generally connected with the formation of inactive or disturbing by-products. In the cases des- cribed by other authors such catalysts still contain without exception free excess TPPTS» which greatly changes the reactivity of the actual TPPTS complex compound. The use of pure TPPTS complex compounds has shown that this class of compound is catalytically active to a much greater degree than was previously known or expected. Thus the claimed complex compounds are excellent hydro¬ génation catalysts. For example» they are successfully used for the hydrogénation of olefins to saturated hydrocarbons. In their presence the reaction takes place at normal pressure and temperatures between and 40oC. The new compounds also cause the water gas equilibrium CO + H20ç=C02 + H2 to shift towards the formation of hydrogen and carbon dioxide. They permit-carrying out the reaction at room temperature and a pressure of approximately 1.5 MPa. Hydrogen formed in this manner can/ for example, be used for catalytic hydrogénations.; e.g. the reaction of organic nitrocompounds to form organic amines. Since with the above-cited reaction carbon monoxide is always present in addition to hydrogen the gas mixture can also be used for the hydroformylation of olefins. The preparation of hydrogen from water and carbon monoxide in the presence of the claimed compounds as catalysts also permits the hydrocarbonylation of ole¬ fins. Particular mention should be made of the fact that the reaction takes place at relatively low temper- atures. Thus/ for example, diethylketone is obtained from ethylene at 140 to 150oC according to the fol¬ lowing equation: H2C=CH2 + CO + H2- > H5C2 - CO - C Furthermore/ the new complex compounds can be used as catalysts for the hydroformylation of olefinically unsaturated compounds. They have proved useful both for the reaction of linear and cyclic olefins and for the reaction of compounds which contain not only a double bond but also functional groups in the molecule. The oxidation of different classes of compounds is also catalyzed by the new compounds containing TPPTS as a complex ligand. Thus»with iodosylbenzene as an oxidant, the corresponding ketones are obtained from secondary alcohols/ epoxides from olefins and diketones from alkines. V,. The complex compounds according to the invention also catalyze reactions in which new carbon-carbon bonds are formed. An example of this type of reaction is the allene-alkine coupling according to * R OOCHX + HC=CR3 -V ROC-CH-CslCR3 + MX where R , R and R are alkyl and/or aryl groups, and R also hydrogen. An example of this reaction is the reaction of 1-bromoallene with phenylacetylene, which takeslplace at room temperature under the catalytic influence of the new compounds. Finally/ the claimed complex compounds catalyze the addition of secondary organic amines to carbon-carbon double bonds according to R1R2C=CH2 + HNR3 V R1R2CII-CH2-NR3 The substituents R1, R2 and R3 have the meanings men¬ tioned above. The following examples describe the preparation and properties of the new compounds. TPPTS was prepared and purified according to the process described in the DE 32 35 030 Al, published Mar. 22, 1984. OPCCôIU-m-SOSNa, referred to as TPPOTS in the following, is separated by means of gel chromatography using the process described in the German patent application P 22 036.9. The yields indicated relate to the puriried substances. The following abbreviations were used in the NMR and IR data taken to characterize the new substances: 200444/ s = singlet, d » doublet, t = triplet, m = multiplet , vw = very weak, w = weak, m = medium, st «= strong, vst » very strong, b.*(= broad band, sh shoulder. The Sephadex*gels used for chromatographic purification of the new substances are dextranes cross-linked with epichlorohydrin. Fractogel is an oligoethylglycol- glycydyl/methacrylate/pentaerythritol dimethacrylate copolymer. Example 1: Synthesis of (n-C-H- )Mn(CO) 0 (TPPTS) • 3 [)_0 and (rt-C5H5)Mn(CO) (TPPTS),* 6 fl 0 l 2 1.05 g (5 mmol) of (a -C5H5)Mn(CO)3 ("Cymantren"*) are dissolved in 70 ml of tetrahydrofuran. The yellow solution is irradiated in a radiation lamp made of duran glass (water-cooled high-pressure mercury lamp TQ 150 manufactured by Original Quarzlampen Gesell- schaft mbH, Hanau) for 90 minutes at IS'C. The carmine red solution is then added to a solution of 1.42 g (2.5 mmol) of TPPTS in 10 ml of water. It is stirred for 16 hours, during which the organic phase loses its color and the aqueous phase turns orange. After the phases have separated, the aqueous phase is washed twice/ in each case with 25 ml of n-pentane and the water is then evaporated in a vacuum. The two compounds contained in the residue are separ¬ ated by column chromatography on Sephadex*G-15. The first, yellow-orange zone contains the hydrated di- phosphane complex (a5-C5H5)Mn(CO){TPPTS>2, the second * trade-mark yellow zone contains the hydrated monophosphane complex (<\?- C5H5)Mn(CO)2(TPPTS) in addition to free TPPTS. Characterizatlon (rZ5-C(.H1.)Mn(CO) (TPPTS)-, • 6 Ho0 31 2 2 P-NHR (109.3 MHz, DjOr 5 •C).t.<» 94.9 ppm (s) . 1H-MR C270 MHz, D20, 5 "C):<f= 3.97 ppm ts,C5[l5,5Q] ; » 7.11-7.99 ppm tinfC6H4, 24H]. IB (cm-1, KBr): v(CO) = 1820 (st); v(SO) = 1221 (sh, vst), 1197 (vst), 1039 (vst), 624 (vst). Elément analysis (c42H41MnNa6o25P2? 1200.61) Calc. C 36.22 H 2.97 Mn 3.94 O 28.71 P 4.45 S 13.81 Found C 36.15 H 2.68 Mn 3.85 O 27.14 P 4.67 S 14.00 CharacterJZ-aiiûn (a5-c5H5)Mn(co)2(TPPTS) • 3 h2o 31P-NMR (109.3 MHz, D20, 5 0C): <£ » 95.7 (s) 1H-HMR (270 MHz, D20, 5 0C): / = 4.36 (s, CgHg, 5H], S " 7.37-8.07 [m, C6H4, 12H]. IB (cm-1, KBr): v(CO) = 1929 (vst), 1852 (vst); v(SO) = 1224 (sh, vst), 1199 (vst), 1040 (vst), 622 (vst). Example 2: Synthesis of Pe(CO),(TPPTS),• 6 H00 and Fe (CO) 4 (TPPTS) • 3 H20 d. I 470 mg (1.3 mmol) of enneacarbonyldiiron, Fe2(CO)g, are boiled with a solution of 587 mg (1.3 mmol) of TPPTS in 50 ml of distilled water for 30 minutes with reflux. An orange-coloured solution forms which is filtered off from the green dodecacarbonyltriiron, Fe3(CO)12, which also forms. The filtrate is concen¬ trated to 10 ml and subjected to column chromatography on Sephadex*G-15. Five zones form, the first two being collected: WT' 1st fraction: Fe(CO)3(TPPTS)2 . 6 H20/ yellow solid, Yield 669 mg (38 %). Characterigation 3:LP-NMR (109.3 MHZf D2Of +28 0.C) \u£ = 74.76 ppm IB (cm-1, KBr): 1885 vst (vCO) Element analysis (CHFeNagOSg; 1383.28) Calc. C 31.36 H 2.86 Fe 4.00 P 4.50 Found C 33.80 H 2.80 Fe 3.42 P 4.09 2nd fraction; Fe(CO)4(TPPTS) • 3 H30/ orange solid. 30 Yield: 167 mg (16 %). Characterization 31P-NMR (109.3 MHz, D20, +28 0C): £= 84.95 ppm IE (cm"1/ KBr): 2050 vstf 1977 vst, 1944 vst (vCO) Element analysis (C22H18FeNa301gPS3; 789.49) Cale. C 35.88 H 2.27 P 3.92 Fe 7.06 Found C 34.30 H 2.46 P 4.40 Fe 6.90 Example 3: Synthesis of Ru(NO)2(TPPTS)2 • 6 H20 Variant A. A boiling solution of 1.71 g (3 mmol) of TPPTS in 25 ml of ethanol and 15 ml of water is mixed with 0.13 g (0.5 mmol) of RuCl3' 3 H20 in 10 ml of ethanol. Then a solution of 100 mg (2.6 mmol) of NatBH.] in 10 ml of ethanol is slowly added dropwise of the solution). Then 210 mg (1.0 mmol) of Diazald * (N-methyl-N-nitroso-p-toluene sulfonamide)* dissolved in 10 ml of ethanolr and the rest of the sodium boran- ate solution are added quickly. The mixture is boiled for another 10 minutes with reflux and then cooled to room temperature. A reddish brown precipitate is formedr which is filtered off through a glass sinterr washed with ethanol and purified by column chromato- graphy on Sephadex*G-15. From, thé first grey-black zone a black substance is isolated (5 mg) whose IR spectrum contains not only v(SO) vibrations of tppts but also bands at 1961 (s) and 1847 On). The desired ruthenium complex is then recovered from the red zone which follows immediately. Yield: 370 mg (53 %); red crystals. VaCiUnt Pt 0.13 g (0.5 mmol) of RuCl3 * 3 tUO in 10 ml of ethanol» 2 ml of triethylamine and 20 0 mg of Diazald in 10 ml of ethanol are added to a boiling solution of 1.71 g (3 mmol) of TPPTS in 20 ml of ethanol und 10 ml of water. After another 3 ml of triethylamine have been added/ the reaction mixture is boiled for another 5 min under reflux. Then it is left to cool to room temperature/ filtered through a glass sinter and the solvent is removed from the filtrate in a vacuum. The raw product is purified by column chrom¬ atography on Sephadex*G-15. Yield: 430 mg (62 %)? red crystals. Characterization 31P-MMR (109.3 MHz, D20, 5 0C) : /= 56.0 ppm (s). IE (KBr# cm" ): v(SO) = 1224 (sh/ vst) / 1199 (vst) , 1040 (vst)/ 624 (vst); v(NO) = 1675 (st). Element analysis (c36H35N2Na6026p2RuS6? 1405-99) Calc. C 30.75 H 2.58 N 1.99 0 29.59 P 4.41-Ru 7.19 S 13.68 Pound C 30.56 H 2.76 N 1.68 0 28.84 P 4.11 Ru 7.01 S 14.72 Example 4: Synthesis of RuCl0(TPPTS)0 • 6 H«o 2 2 Vaciant ft; At room temperature 1.42 g (2.5 mmol) of TPPTS in 15 ml of water are added to 130 mg (0.5 mmol) of ruthenium(IIl)-chloride-trihydrate/, RuCl3 • 3 h o, with vigorous stirring» then heated to 50 "C (bath temperature) and left to react at this temperature for 24 hours. Then the water is removed from the clear brown solution in an oil-pump vacuum. The residue is purified by column chromatography on Sephadex*G-15. Yield: 430 mg (61 %); brown crystals. Variant Pi 570 mg (I mmol) of TPPTS in 10 ml of water are added to a solution of 120 mg (0.2 mmol) of di- chlorotetrakis(triphenylphosphane)ruthenium RuCl9- tP(C6H5)3l4 in 20 ml of toluene and the two-phase system formed is stirred for 15 hours at room temper¬ ature. After the phases have separated the organic phase is washed twicer in each case with 5 ml of water. The combined aqueous phases are extracted twice/ in each case with 5 ml of toluene. Then the water is removed in an oil-pump vacuum. The raw product is purified by column chromatography on Sephadex*G-15. Yield: 160 mg (57 %); brown crystals. Characterization 31P-NMfi (109.3 MHz, D20, 5 0C) : 4- 57.0 ppm (s). IB ;"\' (KBr, cm"1): v(S0) « 1223 (sh, vst) , 1198 (vst)/ 1039 (vst) Element analysis (c36H36ci2Na6024p2Ru56; 14i6.89) Calc. C 30.52 H 2.56 P 4.37 S 13.58 Found C 31.12 H 2.84 P 4.21 S 14.04 Example 5: Synthesis of Co0(CO),(TPPTS)„. G Ho *• D 2 2 100 nig (0.3 mmol) of octacarbonyl dicobaltf Cp2(CO)Rf are dissolved in 10 ml of toiwen*. 400 mg (0.7 mmol) of TPPTS in 10 ml of water are added to the solution and it is stirred for 3 hours at room température. After the phases have separated, the organic phase is washed twice, in each case with 5 ml of water/ and the combined aqueous phases are washed twice, in each case with 5 ml of toluene. The water is removed in a vacuum and the raw product is purified by column chromato¬ graphy on Sephadex*G-25. Yields 370 mg (81 %); brown powder. Characterization 31£zm£ (109.3 MHz, D20, 5 «O : </"= 68.8 ppm (s) IB (cm-1, KBr)s v(CO) - 1954 (vst); v(SO) 1224 (sh, vst), 1200 (vst), 1039 (vst), 623 (vst). Element ana]valb (c42H36Co2Na6p2o30s6; 1530-84) Calc. C 32.95 H 2.37 O 31.35 P 4.05 S 12.57 Found C 32.44 H 2.37 0 31.25 P 3.97 S 12.13 Example 6: Synthesis of CoH(CO)(TPPTS),• 9 H„o A solution of 120 mg (0.5 mmol) of CoCl,» 5 H20 in ml of distilled water is mixed with 1.64 g (3 mmol) of TPPTS and then cooled to 5 0C. After the solids have dissolved with stirring, a solution of 32 mg (0.9 mmol) of NalBH4] in 20 ml of distilled water is added dropwise over a period of 1 hour and at the same time carbon monoxide is introduced. The yellow solution is concentrated in a vacuum to one quarter of its orig¬ inal volume and subjected to column chromatography on Sephadex*G-15. The substance shows hardly any sensiti¬ vity to air. Yield: 856 rag (89 %); canary-yellow powder. Cha r acte riaa Hon „ 31P-NMR (109.3 MHz, D20, 5 0C) : T = 45.93 ppm 1iirMB (270 m3, D20, 5 "O : = 7,32 ppm lm,27K), $ = 7.29 [br, 9H], = -12.35 [q, 2J(P,E1) = 45Hz, 1H] IB (cm" , KBr): 1953 vst (vCoH), 1904 vst (vCO) Element analvais <C55H55CoNa9037P3S9; 1924.99) Calc. C 34.20 H 2.80 Co 3.06 P 4.80 Pound C 34.07 H 2.87 Co 3.09 P 4.76 Example 7: Synthesis of CoH2(TPPTS)3 • 9 U?0 A solution of 120 mg (0.5 mmol) of CoCl-• 5 H20 in ml of distilled water is mixed at 5 "C with 1.64 (3 mmol) of TPPTS. Then a solution of 32 mg (0.9 mmol) of NatBHj] in 40 ml of distilled water is added dropwise with stirring over a period of 1 hour. The solution is concentrated at 5 "C in a vacuum to about 10 ml and subjected to chromatography on a 15-cm-long Sephadex* G-15 column. A high flow rate (approx. 3-4 drops/sec) is chosen and the first part of the red fraction is collected until the zone colour turns green.. Over a prolonged period the substance can be stored in its dry state at normal temperature, but in aqueous solution only at around S8 C. Yield: 0.47 g (50 %); glass-like, red powder. 16- CharagfcpH*pti"n MB, (109.3 MHz, D2Or +28 «O : /= 48.3 ppm (broad) Ji=MB (270 MHz, D20): (CoH) = -12 ppm (very broad) IB (cnf , KBr) : 2008 vst (vCoH) Example 8: Synthesis of Co2(CO)4(HgCg-feC-CgHg)(TPPTS)2 - e n2o 570 rag (1 mmol) of TPPTS in 10 ml of water are added to 250 mg (0.5 mmol) of (/U, £2-diphenylacetylene)hexa- carbonyldicobalt in 20 ml of ethanol and left to boil for 15 hours with reflux. After the mixture has cooled to room temperature, the solvent is removed in an oil- pump vacuum, taken up in 10 ml of water, filtered through a sintered disc and the water is removed in an oil-pump vacuum. The blackish brown residue is purified by column chromatography on Sephadex*G-15. Yield: G10 mg (74 %); blackish brown powder. Characteri-zation 31P-NMR (109.3 MHz, D20, 5 0C) : cT = 51.8 ppm (s) IB (KBr, cm"1): v(CO) = 2017 (vst), 1960 (vst) v(SO) = 1220 (sh, vst), 1195 (vst), 1039 (vst) Element anfllvsisi (c54H46Co2Na6028p2s6? 1653-05) Calc. C 39.24 H 2.80 O 27.10 P 3.75 Pound C 39.55 H 2.67 0 27.16 P 3.68 Example 9: Synthesis of RhCl(TPPTS)- ♦ 9 H20 Variant A. A solution of 260 mg (1.0 mmol) of RhCl3* 3 H20 in 20 ml of water is stirred for about 15 hours after addition of 5.68 g (10 mmol) of TPPTS dissolved in 10 ml of water. The resultant solution, which con- tains still free phosphane (TPPTS), trisdn-sulfo- phenyDphosphane oxide (TPPOTS) as well as small amounts of the binuclear complex K/U-CDRh- (TPPTS)2]2, is purified by column chromatography on Sephadex*G-15. Yield: 1.46 g (73,*). Variant P. In a Schlenk tube 100 mg(0.11 mmol) of chlorotris(triphenylphosphane)rhodium(I), ClRhtp(C6H5)3]3' are dissolved in a mixture of 20 ml of toluene and 10 ml of tetrahydrofuran. 20 ml of an aqueous solution of 1.87 g (3.3 mmol) of TPPTS are added to this solution to form a lower layer. After 12 hours of vigorous stirring the aqueous phase of the two-phase system is washed twice, in each case with ml of methylene chloride. The pure compound is ob- tained by column chromatography on Sephadex*G-15. Yield: 180 mg (82 %). Variant C, lOO mg (0.4 mmol) of bisn.u-chloro) C8H12)12)' are dissolved in 10 ml of methylene chlor- ide. Then 0.68 g (1.2 mmol) of TPPTS in 10 ml of water are added. The two-phase system is stirred intensively for 30 minutes. Then the aqueous phase is isolated and the organic phase extracted twice, in each case with ml of water. The combined aqueous phases are then washed twice, in each case with 5 ml of methylene chloride. The raw product obtained after removal of the solvent is sufficiently pure for most reactions. Depending on the stoichiometry, it can contain small amounts of TPPTS or (a,4-C8H12)Rh2 (/u-Cl)2 (TPPTS)2 which can be removed by column chromatography on Sephadex*G-15. Yield: 740 mg (93 %); red glass-like solid. CharanfcpHifflfrjn 31£zM£ (109.3 MHz, D20, 5 »C) : /. 34.6 ppm (dd) 1J(Rh,PA) = 144.1 Hz cT* 52.8 ppn (dt) t1J(RhrPB) = 195.0 Hz ; -i J(PA/PB) " 40'C.Hz:J IB(cm~ , KBr) v(SO) 1206 (shr vst), 1181 (vst), 1027 (vst)f 741 (vst), 545-(vst), 490 (vst) Element anfllvaifi Cc54i-i54ciNa9036P3Rh s9; 2005.71) Calc. C 32.34 H 2.70 P 4.63 0 Found C 32.30 H 2.71 P 4.60 Example 10: Synthesis of Rh(NO) (TPPTS),. 9 11 0 Variant A. 0.37 g (0.4 mmol) of Rh(NO) [P(C6I15)3] ara dissolved in 40 ml of toluene. Then 2.27 g (4 mmol) of TPPTS in 20 ml of water are added and the resultant two-phase system is stirred for 24 hours at 25 0c. After this time the organic phase has more or lees lost its colour. The phases are separated and the organic phase is washed twice, in each case with 5 ml of water. The combined aqueous phases are filtered. Then the water is evaporated in a vacuum. The residue is puri¬ fied by column chromatography on Sephadex*G-25. Yield: 0.58 g (73 %); dark-red crystals. Variant dt 0.26 g (I mmol) of RhCl3.3 H20 in 20 ml of ethanol, 0.40 g (1.9 mmol) of DiazaldR in 20 ml of ethanol und 0.30 g (7 mmol) of sodium hydroxide in ml of water and 10 ml of ethanol are added in quick succession to a boiling solution of 5*68 g (10 mmol) of TPPTS in a mixture of 40 ml of water and 40 ml of ethanol. The mixture is left to boil for 15 minutes under reflux and cooled to room temperature. After 19- careful neutralisation of the alkaline solution with concentrated sulfuric acid/ the water is evaporated in a vacuum. The residue is washed twicer in each case with 10 ml of ethanol. The raw product is purified by column chromatography on Sephadea*G-25. yield: 1.51 g (76 %); dark-red crystals. Variant C» 1.14 g (2 mmol) of TPPTS in 10 ml of water are added to a suspension of 220 mg (0.3 mmol) of Rh(NO)Cl2[P(C6H5)3]2 in 15 ml of methylene chloride and the resultant three-phase system is stirred for hours at 25 "C. After this time the rhodium complex has completely dissolved and the organic phase has more or less lost its colour. After the phases have separated, the organic phase is washed twice/ in each case with ml of water/ and the combined aqueous phases are washed twice, in each case with 5 ml of methylene chloride. Then the water is evaporated in a vacuum. The raw product is purified by column chromatography on Sepha- dex*G-25. Yield: 420 mg (70 %); dark-red crystals. CharacterlsaUfln 31P-NMB (109.3 MHZ/ p20, 5 •0;/= 48.4 ppm (d) [(Rh/P) - 176.6 Hz], IB (cm-1; KBr) : v(S0) = 1225 (sh, vst) , 1200 (vst) , 1039 (vst)/ 623 (vst). Elément anaJysIn (c54H54Na9No37P3Rhs9; 2000.28) Calc. C 32.43 H 2.72 N 0.70 O 29.60 P 4.65 Rh 5.14 S 14.42 Found C 32.61 H 2.68 N 0.60 0 30.90 P 4.54 Rh 5.0 S 14.23 Example 11: Synthesia of Rh(CH-COO)(TPPTS), • 9 e o A solution of 600 mg (1.05 mmol) of TPPTS in 10 raL of water is added to a solution of,100 mgCO.ll mmol) of Rh(CH3COO)tP(C6H5)3]3 in 10 ml of methylene chloride. After 24 hours of stirring, the aqu.eous phase Is iso¬ lated and its contents subjected to chromatography on a column packed with Sephadex*G-15. Yield: 30 mg (15 %); red powder. Charantprgtjnn 3:i£=MB (109.3 MHz, D20, 5 0C) : /= 34.5 ppm (dd) [(Rh,? m 144.1 Hz] ef= 53.0 ppm (dt) [(RhjPg) = 195.3 J<PA'PB> = 40.9 Hz] Uz ; Element anfllYRis «gHNaRh s9: 2029.30) Calc. C 33.15 H 2.83 Na 10.20 Rh 5.07 Pound C 33.15 H 2.80 Na 10.00 Rh 5.10 Example 12: Synthesis of Rh(CO) (OH) (TPPTS), • 6 II O Variant fli 100 mg (0.39 mmol) of solid [Rh(CO)2acac] (acac - acetylacetonate) are added to a solution of 2.2 9 (3.88 mmol) of TPPTS with vigorous stirring and after 12 hours evaporated to dryness in a vacuum. The resi¬ due is taken up in a little water and purified by chromatography on Sephadex*G-15. Yield: 310 mg (58 %); reddish brown glass. Variant P; A solution of 250 mg (0.12 mmol) of RhH(CO)- (TPPTS)3 • 9 H20 in 20 ml of water is heated to boiling for 12 hours with reflux. Then the reaction mixture formed is separated by column chromatography on Sepba- dex*G-15. Yield: 110 mg (63 %); reddish brown glass. Character!mtinn. £=mE (109.3 MHz, D20, 21 "O : / = 31,8 ppm (d) ["•JCRh/P) = 128.5 Hz] IB (KBr, cm"1): v(C0) 1989,.:,v(SO) 1196 (sh, st) 1040 (vst) 994 (st), 791 (st), 690 (m) Bletngnt anlypif? (c37H37Na6o26P2Rhs6; 1392.82) Calc. C 31.90 H 2.68 0 29.86 S 13.81 P 4.45 Rh 7.38 Found C 32.56 H 2.73 0 30.13 S 14.57 P 4.38 Rh 7.21 Example 13: Synthesis of Rh(CO)Cl(TPPTS), - G H 0 Variant A: In a Schlenk tube 1.84 g (1.0 mmol) of RhCl(TPPTS)3 • 9 H20 are dissolved in 4 0 ml of nitrogen-saturated water. A red solution is obtained, into which carbon monoxide is introduced over a period of 10 minutes via a gas feed pipe equipped with a sintered disc. The solution becomes much clearer as soon as the carbon monoxide is introduced. After col¬ umn chromatography of the raw substance on Sephadex*G- the rhodium complex is obtained in an analytically pure form. Yield: 1.22 g (95 %); yellow glass. Characterisation 31£=MB (109.3 MHz, D20, 5 0C) : / = 31.4 ppm (d) JCRhfP) = 129.8 Hz] IB (cm-1, KBr): v(CO 1979 (vst), 1639 (st), v(SO) 1211 (sh, vst), 1150 (vst), 1041 (vst), 789 (st) Element anaiysip (c37H36025clNa6p2Rh V 1411-2'7) Calc. C 31.49 H 2.57 Cl 2.51 0 28.34 P 4.39 Rh 7.29 S 13.63 Found C 31.50 H 2.70 Cl 2.50 0 29.94 P 4.14 Rh 7.30 S 13.95 s f Variant B. lOO mg (0.25 ramol) of tetracarbonylbis( u- chloroîdirhodiumr t(CO)2RhCl]2, are dissolved in 10 ml of toluene. 570 mg (1.0 mmol) of TPPTS in 10 ml of water are added and the resultant two-phase system is left to stir for 15 hours at room temperature. After this period the organic phase has lost its colour. The phases are separated and the organic phase is washed twice» in each case with 5 ml of waterr the combined aqueous phases are washed twice, in each case with 5 ml of tolijene. Then the water is removed in an oil-pump vacuum. The raw product is purified by column chromato¬ graphy on Sephadex*G-15. Yield: 590 mg (84 %); yellow powder. Characterization 31P-NMR (109.3 MHz, D20, 5 0C) : /= 31.3 ppm (d) & [(Rh/P) = 128 Hz] <|; IB (KBr, cm x) : v(CO) - 1980 (vst) t v(SO) - 1224 (shr vst)f 1199 (vst), 1040 (vst) Element analysis (c37H36025clNa6p2Rhs6; 141]'27) Calc. C 31.49 H 2.57 Cl 2.51 O 28.34 P 4.39 Rh 7.29 S 13.63 Found C 32.05 H 2.53 Cl. 2.64 0 28.26 P 4.14 Rh 7.30 S 13.95 Example U: Synthesis of Rh(OH)(TPPTS)3 • 9 H20 A solution of 260 mg (1.0 mmol) of RhCi3 • 3 H20 in ml of water is stirred for approx. 15 hours after the addition of 5.68 g (10 mmol) of TPPTS dissolved in ml of water. The solution formed containing RhCl- (TPPTS)3, free TPPTS, TPPOTS as well as small amounts of a binuclear complex [Rhu-CD (TPPTS)212 is left to stand for at least 24 hours at room temper¬ as- ature and then worked up by column chromatography on Sephadex*G-15. After the solvent has been removed, the chlorine-free complex Rh(OH) (TPPfS)3 '-9 H2O is obtained in yields of 70 to 90 % as red glass. ChararfrpHgat-jpn 31P-NMR (109.3 MHz, D2Or 21 *C) : <f~35.2 ppm (dd) (RhrP » 143.9 Hz cf= 53.48 ppm (dt) ; (RhrPg) = 195.3 Hz 2J(PfP) = 40.9 Hz IB <KBr, cm"1): v(SO) 1220 (sh, vst) , 1196 (vst) , 1038 (vst)f 787 (m). 624 (m), 527 (w) Element analysla (c54H55Na9037p3Rhs9; 1987-25) Calc. C 33.63 H 2.79 Cl 0.0 O 29.79 P 4.68 Rh 5.18 S 14.51 Pound C 32.59 H 2.89 Cl 0.0 O 30.57 P 4.33 Rh 5.90 S 14.10 Example 15: Synthesis of [Rh(/u-Cl)(CO)(TPPTS)]2 • 6 H20 570 mg (1 mmol) of TPPTS in 10 ml of water are added to a solution of 190 mg (0.5 mmol) of bist(.u-chloro)- dicarbonylrhodium],. tRh(/u-Cl) (CO) 2]2, in 10 ml of toluene and the two-phase mixture thus formed is stir¬ red for 18 hours at room temperature. After separation of the phases the organic phase is washed twicer in each case with 5 ml of water. The combined aqueous phases are extracted twice» in each case with 5 ml of toluene and filtered. The water is removed from the filtrate in an oil-pump vacuum. Purification takes place by column chromatography on Sephadex*G-15. RhCl- (CO)(TPPTS)2 • 6 H20 is isolated from the first orange-coloured zone and [RM.u-CD (CO) (TPPTS) ]„ fr< the subsequent yellow zone. Yield: 330 mg (42 %); yellow powder. :om vw-- Characteripigtion JErMB (109.3 MHz, D20, 5 «O : é - 48.2 ppm (d) [ J(Rh,P) - 180 Hz] IB (KBr, cm"1): v(CO) » 1986... (vet) ; v(SO) 1224 (shr vat)f 1197 (vst), 1039 (vst) Element anfllynln (C38H36ci2Na6o26P2Rh2s6; 1577.65) Calc. C 28.93 H 2.30 0 26.37 P 3.93 Rh 13.05 S 12.1! Found C 29.90 H 2.23 0 27.02 P 3.90 Rh 13.15 S 12.0! Example 16: Synthesis of 2(TPPTS)2tP(C6H4S03Na)2(C6H4-m-S03)12 * 10 "2° 850 mg (1.5 mmol) of TPPTS in 10 ml of water are added to a solution of 100 mg (0.25 mmol) of tetrakis( tl2- ethyleneJbist/U-chloroJdirhodiumf [RM.u-CU- 2 ' (H, -C2H4)2]2 in 10 ml of methylene chloride. The two-, phase system is stirred for 30 minutes at room temper¬ ature/ during which the. organic phase loses its colour. After separation of the phases the organic phase is extracted twice/ in each case with 5 ml oC water. The combined aqueous phases are washed twicer in each case with 5 ml of methylene chloride and then filtered. The water is evaporated in an oil-pump vacuum. The raw product is purified by column chromatography on Seph- adex G-25. First comes a grey band which is followed by an orange zone from which the rhodium complex compound is isolated. Yield: 320 mg (49 %); brownish red powder. CharacfcerigafrjJQn 31£zMB (1U9.3 MHz/ D20/ 5 0C) : f = 57.8 ppm (d) [•"JtRh/P) = 181 Hz] IB (KBr/ cm"1): v(SO) = 1224 (shr vst), 1199 (vst), 1139 (vst) 200444Î Element. MMIyhH 72H68O46P4S12Na10Rh2' 2613.63) Cale. C 33.09 H 2.62 Cl 0.00 0 28.16 P 4.74 Rh 7.87 S 14.72 Pound C 33.04 H 2.85 Cl 0.00 0 28.08 P 4.48 Rh 8.00 S 14.16 Example 17: Synthesis of Rh2(/u-Cl)2(-c8H12) (TP (TPPTS)2. 6 H20 A solution of 454 rag (0.8 mmolî of TPPTS in 10 ml of water is added to a solution of 200 mg (0.4 mmol) of tRM/U-Cl) (Q, -C8H12)]2 in 10 ml of methylene chloride. The two-phase system obtained is stirred for 12 hours at room temperature. Then the aqueous phase is isol¬ ated, the organic phase is washed twice, in each case with 5 ml of waterr and the combined aqueous phases are washed twice, in each case with 5 ml of methylene chloride. In order to remove the residual methylene of its original volume. The resultant solution is subjected to column chromatography on Sephadex*G-15. Yield: 510 mg (73 %); orange-red powder. CharacfcP.Hnn 1£=mR (109.3 MHz, D20, 5 «O : </= 129.0 ppm (d) [(Rh,?) =146.2 Hz] OzMR (400 MHz, D20, 23 °C) : /= 2.14 ppm tbr CO. 4H];cf - 2.43 ppm tbr s, CH2, 4H1 ; J = 4.54 ppm tCH, 4H]; g . 7.28-7.96 [m, CgH 24 Hi I£ (cm"1, KBr): 1633 (m), 1399 (st), v(SO) 1206 (sh vst), 1038 (st), 791 (st), 693 (m), 621 .(m; 26- Example 18: Synthesis of Rh,(CO)-(TPPTS)n • 27 H„n 230 mg (0.07 mmol) of RhgCCOjyç.CCgHgïjlg are dissolved in 10 ml of chloroform. 1.42 g"<2-.5 mmol) of TPPTS in ml of water are added with stirring, whereupon the aqueous phase quickly turns yellow. To complete the exchange reaction» the mixture is stirred for another hour and the two phases separated. The organic phase is washed twicer in each case with 5 ml of water. Then the aqueous phases are combined and the water is removed in a vacuum. The residue is purified by column chromato¬ graphy on Sephadex*G-25. Yield: 350 mg (78 %); yellow¬ ish brown powder. Characterisation 31P-NMR (109.3 MHz, D2Of 5 0C): £ = 30.5 ppm [1J(Rh,P) IS =130 Hz]. -1 IE (cm , KBr): v(SO) = 1225 (shr vst), 1200 (vst), 1039 (vst), 623 (vst); v(CO) = 1981 (st) Element analysis (ci69Hi62Na270ii5I>9Rh6s27; 6415-61) Calc. C 31.64 H 2.55 0 28.68 P 4.35 S 13.49 Found C 31.96 H 2.93 0 28.83 P 4.29 S 13.69 Example 19: Synthesis of Ir(NO)(TPPTS)3 • 9 H20 850 mg (1.5 mmol) of TPPTS in 10 ml of water are stirred into a solution of 140 mg (0.17 mmol) of dichloronitrosylbis(triphenylphosphane)iridium, IrCl2NO [P(C6H5)3]2 in 30 ml of methylene chloride at room temperature. After only a short time the aqueous phase turns brown whilst the organic phase loses its color. To complete the reaction the mixture is stirred for another hour and the phases are then separ¬ ated. The organic phase is washed twice» in each case with 5 ml of water. The combined aqueous phases are extracted twice/ in each case, with 5 ml of methylene chloride and then the water is evaporated in an oil- pump vacuum. The raw product is purified by column chromatography on Sephadex*G-25 or Fractogel* TSK HW-4 0 P. Yield: 160 mg (45 %); brown powder. Characterization 31P-HMR (109.3 MHz, D20, 5 0C) : S " 16.7 ppm (s) IB (KBr, cm" ): v(SO) 1225 (shr vst) , 1190 (vst) , 1039 (vst)r 623 (st) Element analysis (C54H54IrNNa9037P3S9; 2089.59) Calc. C 31.04 H 2.60 Cl 0.0 N 0.67 0 28.33 P 4.45 S 13.81 Pound C 29.42' H 2.55 Cl 0.0 N 0.61 O 27.90 P 3.90 S 13.41 Example 20: Synthesis of IrCl(CO)(TPPTS)3 . 9 H20 160 mg (0.5 mmol) of Ir(CO)3Cl are suspended in 20 ml of toluene. With vigorous stirring 1.14 g (2 mmol) of TPPTS in 10 ml of water are added at room temperature. After only a short time the aqueous phase turns yellow. To complete the CO substitution» the mixture is stirred for another 24 hours at room temperature and the phases are then separated. The organic phase is washed twice, in each case with 5 ml of water. The combined aqueous phases are extracted twicer in each case with 5 ml of toluene and then filtered. After the solvent has been removed in an oil-pump vacuum/ the raw product is purified by column chromatography on Sephade/G-15. Yield: 600 mg (57 %); orange-yellow powder. 31P-NMR (109.3 MHz, D.O, 5 0C): <f = -2.8 ppm (s) Characterigation IE (KBr, cm-1): v(CO) = 2005 (m), 1963 (m) v(S0) = 1226 (shr vst), 1200 (vst), 1038 (vst), 623 (vst) ,; Blgmgnt analysis (c55H54ciirNa9o37P5s9; 2123.05) Calc. C 31.11 H 2.56 Cl 1.68 Ir 9.05 O 27.88 P 4.38 Found C 30.04 H 2.54 Cl 1.67 Ir 8.76 0 28.13 P 3.99 Example 21: Synthesis of IrH(CO)(TPPTS)3 • 9 H20 290 mg (0.5 mmol) of TPPTS in 10 ml of water are added to 200 mg (0.2 mmol) of carbonylhydridotris(triphenyl- phosphane) iridium, IrH(CO)[P(C6H5)3]3, dissolved in ml of toluene. The resultant two-phase mixture is left to boil for 5 days with reflux. After it has cooled to room temperature, the phases are separated and the organic phase is extracted with 10 ml of water. The combined aqueous phases are washed twice, in each case with 10 ml of toluene and then filtered. The water is evaporated from the filtrate in an oil-pump vacuum. Yield: 310 mg (89 %, related to TPPTS); yellow powder. Characterization J P-NMR (161.9 MHz, D20, 5 0C) : <£= 19.2 ppm (s) 1H-NMR (400 MHz, D20, 5 0C) : § = -10.69 ppm (q, Irll, 1H) [2J(P,H) = 20.8 Hz] §= 7.08 - 7.76 ppm (m, C6H4, 12H) IE (KBr, cm"1): v(IrH) = 2128 (w), v(CO) = 1927 (m), v(SO) = 1222 (sh, vst), 1196 (vst), 1038 (vst) 200444Î Element analyfiin (c55H55IrNa9o37P3s9; 2088.61) Calc. C 31.63 H 2.65 0 28.34 P 4.45 Found C 31.65 H 2.53 0 28.23 P 4.08 Example 22: Synthesis of (rç,4-C8H12)Ir(Cl) (TPPTS)2 • 6 H20 570 rag (1.0 mmol) of TPPTS in 10 ml of water are stirred into a solution of 130 mg (0.2 mmol) of K/U-CDlrty -C8H12)]2 in 10 ml of toluene at room temperature. The organic phase loses its colour spon- I taneously. To complete the reaction, stirring is con¬ tinued for another 15 minutes. After separation of the phases» the water is evaporated in a vacuum. The raw product is purified by column chromatography on Sepha- dex*G-15. Yield: 770 mg (97 %); red crystals. Characterisation 31P-NMR (109.3 MHz, D20, 5 0C) : $= 19.0 ppm (s) 1H-MMR (270 MHz/ D20, 5 0C) : g = 1.89 ppm [br, d, 411, 2J(HrH) = 7.8 Hz» CH2], = 2.33 ppm tbr, s, 4Hf CH2]; 5= 4.32 ppm [br s, 4H, CHI ; S 7.48-7.96 ppm [m, 24Hf CGH4] IB (cm"1/ KBr): v(SO) = 1223 (sh, vat), 119D (vst)/ 1039 (vst), 623 (vst) Element analvsic! (C44H48ClIrNa6024P2S6 ; 1530.77) Cale. C 33.43 H 3.OS CI 2.24 O 24.29 P 3.92 3 12.17 Found C 33.56 H 2.99 Cl 2.26 0 23.75 P 3.63 S 12.37 Example 23: Synthesis of Ni(TPPTS),« 9 no Variant A. 71 mg (0.3 mmol) of NiCl2 . 6. HO and 0.35 g (1.5 mmol) of TPPTS are dissolyèd in a"mixture of 5 ml of water and 5 ml of ethanol. At -15 0C 34 mg (0.9 mmol) of Na[BH4], dissolved in 5 ml of water and 5 ml of ethanol/ are added dropwise over 90 minutes. The reaction solution turns red and then reddish brown. After all the Na[BH4] has been added, the temperature of the solution is allowed to rise to room temperature over a period of 3 hours and the solvent is removed in a vacuum. The raw product is purified by means of column chromatography on Sephadex*G-15r the column being cooled to 0 0C. Yield: 0.53 g (92 %); reddish brown powder. CharacfceHaaHng 3:LP-NMR (109.3 MHz, D20/C2H5OH 1:1, -30 0C) : / 22.7 ppm (s) . The chemical shifting of Ni(TPP)3 is <£ = 23 ppm IC. A. Tolman, W. C. Seidel and D. H. Gerlach, J. Am. Chem. Soc. 94 (1972) 26691. (KBr, cm"1): v(SO) - 1222 (s (vst)r 1039 (vst)/ 622 (vst) IB (KBr, cm"1): v(SO) = 1222 (sh, vst), 1192 Element analysis (c54H54Na9Ni035p3s9: 1926.07) Cale. C 33.67 II 2.33 P 4.82 Ni 3.05 P 4.02 Pound C 33.74 H 2.87 P 4.69 Ni 3.00 P 4.79 Variant B. 830 mg (1.45 mmol) of TPPTS in 10 ml of water are stirred vigorously into a solution of 100 mg (0.36 mmol) of bis(rç, -1.5-cyclooctadiene)nickel NUrç, ~C8IIi2)2 in 10 ml of toluene,, the aqueous solu¬ tion rapidly turns reddish brown. To complete the exchange reaction/ the two-phase system is stirred for another 8 hours at room temperature/ after which the organic phase has lost its colour. The phases are separated. The organic phase is washed twice/ in each case with 5 ml of water» and the-, combined aqueous phases are extracted twice/ in each case with 5 ml of toluene. Then the water is evaporated in a vacuum. The residue is purified by column chromatography on Sepha- dex*G-15 at 0 0C (glass column/ 1 = 60 cm/ d 1 cm, cooling with Kryomat Julabô*F 40/ (a circul¬ ating cryomat manufactured by Julabo). After a green zone containing decomposition products/ there follows a broad/ reddish brown zone from which the nickel complex is isolated. Yield: 380 mg (55 %); reddish brown powder. Characterizahinn 31£rMB (109.3 MHz/ DjO/COH 1:1, -30 0C) : S = 22.7 ppm (a) The chemical shifting of Ni(TPP)3 is fi = 23 ppm IC. A. Tolman/ W. C. Seidel and D. h. Gerlach/ J. Am. chem« Soc. 94 (1972) 2669]. (KBr, cm"1) : v(SO) = 1039 (vst)/ 622 (vst) IB (KBr/ cm"1): v(SO) = 1222 (sh, vst)/ 1192 (vst), Yaciant C, 580 mg (1.2 mmol) of TPPTS in 10 ml of water are stirred into a solution of 330 mg (0.3 mmol) of tetrakis(triphenylphosphane) nickel/ Ni [P(C,lll. ) 3)./ in ml of toluene at room temperature. The aqueous phase rapidly turns reddish brown. To complete the exchange reaction stirring is continued for another 15 hours and then the phases are separated. The organic phases are washed twice, in each case with 5 ml of water, the combined aqueous phases are extracted twice/ in each case with 5 ml of toluene. Then the water is removed in an oil-pump vacuum. The raw product is purified by 32- column chromatography on Sephaâex*G-15. Yield: 35 0 rng (61 %); reddish brown powder. Characterisation 31P-NMR (109.3 MHz, DjO/CjHgOH? -'SJO 0C):'<= 22.7 ppn (s) The chemical shifting of Ni(TPP)3 isj= 23 ppn [C. A. Tolman» W. C. Seidel-and D. H. Gerlach/ J. Am. Chem. Soc. 94 (1972) 2669]. IB (KBrr cm"1): v(SO) = 1222 (shr vst), 1192 (vst), 1039 (vst), 622 (vst) RlpmPnt analysis (C54BI54Na9Ni03(5P3S9 ; 1926.07) Cale. C 33.67 H 2.33 Ni 3.05 P 4.32 O 29.90 Found C 33.74 H 2.87 Ni 3.49 P 4.69 O 30.61 Example 24: Synthesis of Ni(CO)2(TPPTS)2 • 6 HjO Variant A. 170 mg (1 mmol) of Ni(CO)4 are dissolved in 10 ml of toluene and mixed with 2.84 g (5 mmol) of TPPTS, dissolved in 10 ml of water. The resultant two- phase mixture is stirred for 18 hours at 25 CC. The aqueous phase is washed with 10 ml of toluene and then the water is removed in a vacuum. The raw product is purified by gel chromatography on Sephadex*G-15 (col¬ umn 1 = 100 cm, d = 24 mm). Yield: 0.83 g (61 %); yellow powder. çhflçstçterization 31P-NMR (109.3 MHz, D20, 5 0C): § = 34.9 ppm (s) :5 IB (cm"1, KBr) : v(C0) = 1944(st)r 2008(st); v(SO) = 1122(sh, vst), 1196(vst)r 1040 (vst), 624(st) Element analysis (C38H36Na6NiP2026S6; 1358.63) Calc. C 33.57 H 2.67 Ni 4.32 0 30.60 P 4.56 Found C 33.52 H 2.52 Ni 4.52 0 29.23 P 4.25 33- "> il i tmÊÊÊmumÊÊmuSKi Vaci,9nt Pi A CO gas stream is passed through a solur tion of 190 mg (0.1 mmol) of Ni(TPPTS) • 9 HO In ml of water at room temperature for 15 minutes; the original deep reddish brown s.olafcion rapidly turns yellow. Then stirring is continued for another IS minutes and the solvent is then removed in an oil-pump vacuum. The residue is purified by column chromato¬ graphy on Sephadex*G-15. Yield: 110 mg (81 %); yellow powder. Charactgri7.atn 31£zMB (109.3 MHz/ D20/C2H50H 1:1, -30 0C>:/« 22.7 ppm (s). The chemical shiftin of Ni(TPP)3 is J"= 23 ppm [C. A. Tolmam W. C. Seidel and D. n. Gerlachr J. Ara. Chem. Soc. 94 (1972) 2669] (KBrr cm ) : v(S' (vst)/ 622 (vst) 1% (KBr' cm~ >i y(SO) 1222 (sh, vst), 1192 (vst), 1039 Element analysis (c38H36Na6Nip2026s6? 1358'63) Calc. C 33.57 H 2.67 Ni 4.32 0 30.60 P 4.56 Pound C 33.52 II 2.52 Ni 4.52 O 29.23 P 4.25 Example 25: Synthesis of Ni(PP3)2 (TPPTS),» 6 11,0 VaEiUnt At 0.21 g (0.5 mmol) of Ni(PF3)4 are dissolved in 20 ml of tetrahydrofuran. 0.85 g (1.5 mmol) of TPPTS in 10 ml of water are added to the solution and it is heated over a period of 4 hours to boiling point. The aqueous phase has then turned yellow. After cooling to room temperature, the phases are separated and the water phase is washed twice, in each case with ml of toluene, and the solvent is then removed in a vacuum. The raw product is purified by column chroraa- tography on Sephadex*G-15. Yield: 0.56 g (76 %); yel¬ low powder. VarJLgnt B., 0.13 g (0.3 mraol) of Ni(PF3)4 are dissolved' in 10 ml of tetrahydrofuran aijd UO ml of toluene. Then 0.51 g (0.9 ramol) of TPPTS in 10 ml of water are added and the resultant two-phase mixture-is stirred for 3 hours at 250C. After this period the aqueous phase has turned yellow. The phases are separated the aqueous phase is washed twice/ in each case with 5 ml of tol- uene, and evaporated until dry. The raw product is purified by column chromatography on Sephadex*G-15. Yield: 0.35 g (70 %); yellow powder. Charant-.PHggfjrffl SzMM (109.3 MHz, D20/EtOH 1:1, -30 0C) : <f = 45.0 ppn. BXement gnglypifl (c36H36F6Na6Ni024p4s6; :]L479-55) Calc. C 29.23 H 2.45 P 7.71 Ni 3.97 O 25.95 P 8.37 S 13.00 Found C 29.10 H 2.50 F 7.60 Ni 3.89 O 26.15 P 8.50 S 13.50 Example 26: Synthesis of Pd(TPPTS)7 • 9 H o Vflùant A, 2.27 g (4 mraol) of TPPTS in 20 ml of water are added to a solution of 0.46 g (0.4 mmol) of tetra- kis(triphenylphosphane)palladium, PdlPfCgM-] , in ml of toluene at 25 0C. The organic phase rapidly loses its colour. To complete the reaction, stirring is con¬ tinued for another 15 minutes. Then the phases are separated and the toluene phase is washed twice, in each case with 5 ml of water. The combined aqueous phases are filtered, then the water is evaporated in a vacuum. The residue is purified by column chromato¬ graphy on Sephadex*G-25. Yield: 0.41 g (52 %); brown powder. Variant H. 2.84 g (5 mmol) of TPPTS in 10 ml of water are stirred into a solution of 0.32 g (1 mmol) of dipotassium tetrachloropalladate(II), K-lPdCl.lr in lo' ml of water at 25 0C, the reaçtiçin solution turning brown. Then 170 mg (4.5 mmol) of sodium tetrahydrido- borate, Na[BH4], in 5 ml of water are added dropwise over a period of 30 minutes. Stirring is continued for another 90 minutes and then the water is removed in a vacuum. The residue is washed twicef in each case with 5 ml of ethanol, and then purified by column chromato¬ graphy on Sephadex*G-25. Yield: 1.62 g (82 %); brown powder. Charac:tPr-i??Mnr| 31£zMB (109.3 MHz, D20, 5 0C: S = 22.6 ppm (a). IB (cm" , KBr) : v(SO) = 1225 (sh, vst) , 1200 (vst) , 1039 (vst), 622 (vst). SUni?nt analysis <c54H54Na9036p3Pds9' 1973-77) Calc. C 32.86 H 2.76 O 29.18 P 4.71 Pd 5.39 G 14.62 Found C 32.35 H 2.70 0 29.95 P 4.87 Pd 5.30 S 15.27 Example 27: Synthesis of Pt(TPPTS).» 12 H 0 Variant ft,, 0.78 g (0.7 mmol) of tetrakis(triphenyl- phosphane) platinum, Pt[P(C6H5) 3, are dissolved in 80 ml of toluene. 3.18 g (5.6 mmol) of TPPTS in 30 ml of water are stirred into the solution, whereupon the organic phase quickly loses its colour. In order to complete the reaction, stirring is continued for an¬ other 15 minutes at room temperature. After separation of the phases, the organic phase is washed twice, in each case with 10 ml of water. The combined aqueous solutions are filtered the water is removed in a vacuum. The substance is purified by column chromato¬ graphy on Sephadex*G-25. Yield: 750 mg (40 %) ; yellov;- ish orange crystals. Variant D. A solution of 2.84 g (5 ramol) of TPPT5 in a mixture of 10 ml of water and 20 ml- of ethanol is heated to 7Q0C. After 80 mg (2 mmol) of sodium hydrox¬ ide have been added* a total of 0.42 g (1 mmol) of dipotassiumtetrachloroplatinate(II), KtPtCl.]/ in ml of water are added dropwise over a period of 1 hour. The solution turns orange-yellow. Stirring is continued for another 2 hours and the solvent is re¬ moved in a vacuum. The residue is purified by column chromatography on Sephadex*G-25. Yield: 1.21 g (45 ft); yellowish-orange crystals. Variant C. 200 mg (0.24 mmol) of the peroxo-complex Pt((2,2-02) [p(C6H5)3]2 • c6H6 are dissolved in 10 ml of methylene chloride. 1.71 g (3 mmol) of TPPTS in 10 ml of water are added and the resultant two-phase system is stirred for 5 hours at 25 0C. After separation of the phases the organic phase is washed with 10 ml of water. The combined aqueous phases are washed with ml of methylene chloridef then the water is removed in a vacuum and the raw product is purified by column chromatography on Sephadex*G-25. Yield: 240 mg (37 %); yellow crystals. Characterization 31£zMR (109.3 MHz, D20, 5 0C) : /= 22.2 ppm (d) [1J(Pt,P) = 2853 Hz, 3J(P,P) = 19.8 Hz]; J = 24.1 ppm (m) [(Pt-P) = 2210 Hz]. IB (KBr# cm"1): v(SO) = 1226 (sh/ vst), 1201 (vst), 1039 (vst)f 622 (vst) 37- Element analysis (C72H60Na12O48P4PtS12; 2684.94) Calc. C 32.21 H 2.70 0 28.60 P 4.61 Pt 7.27 S 14.33 Found C 32.21 H 2.58 0 27.62 P 4.61 Pt 7.03 S 14.86 Example 28: Synthesis of PtCl2(TPPTS)2 • 6 H20 A solution of 0.21 g (0.5 mmol) of dipotassium-tetra- chloroplatinate(II)/ K2[PtCl4]/ in 5 ml of water is added dropwise at 25 0C to 0.57 g (1 mmol) of TPPTS in ml of water slowly enough to ensure that the colour is always lost. Then the mixture is stirred for hours and the water is removed in a vacuum. The product still contains residual potassium chloride which cannot be separated by means of gel chromatography as the platinum complex quickly decomposes on conventional support materials. Yield: 0.69 g (91 %); yellowish powder. Characterization 31P-NMR (109.3 MHz, D20/ 5 0C): S = 13.9 ppm [1J(PtrP) = 3727 Hz] IE (cm-1, KBr): v(SO) = 1226 (sh, vst), 1201 (vst), 1039 (vst), 623 (vst); v(Pt-Cl) = 313 (w) Example 29: Synthesis of Cu(TPPTS),[u-PfO-H.-m- S03Na)2(C6H4-m-S03)]3 • 12 H20 Z / b 4 A solution of 282.5 mg of TPPTS and 62.4 mg of CuSO.* H20 in 10 ml of distilled water is stirred for 2 hours at room temperature. The originally light-blue solution first turns green and is yellow after the reaction has been completed. The solution is concen- then covered with the same amount of ethanol. After it has been allowed to stand for 3 days at room temper¬ ature, white crystals precipitate. They are separated/ dissolved in 5 ml of distilled water and then sub¬ jected to column chromatography on Sephadex* G-25 (column: diameter 2.4 cm, length 1.20 m). The first fraction is collected. When the eluate is con¬ centrated in a vacuum, white crystals are obtained X0 which soon turn brick-red when left to stand in the air. The yield is 397 mg (40 %). Char antP rlfUrn SzME (109.3 MHz, D20, 28 0C) : £= -2.93 ppm Element analysis CcgoH84cu3o57Na12P5s1 , 3177.62) Calc. C 33.90 H 2.84 Cu 5.90 P 4.80 Pound C 31.99 H 2.97 Cu 5.0 P 3.95 Example 30: Synthesis of Ag(TPPTS)2tP(C6II4S03Na)2(C6H4-in-SO )] . 8 » O yifrnt A; 1.14 g (2 mmol) of TPPTS in 10 ml of water are added to 68 mg (0.4 mmol) of silver nitrate in 5 ml of water and stirred for 7 hours at room temperature, during which time the silver nitrate dissolves com¬ pletely. The water is removed from the clear solution in an oil-pump vacuum. The glassy residue is purified by column chromatography on Sephadex*6-15. Yield: 710 mg (92 %); colourless, slightly light-sensitive powder. Vriar>t Pi i'14 9 (2 mmol) of TPPTS in 15 ml of water are added to 70 mg (0.5 mmol) of silver chloride and stirred for 2 days at room temperature. Afterwards the silver chloride has dissolved, forming the complex compound. The water is removed from the clear solution in an oil-pump vacuum. The glassy residue is purified by column chromatography on Sephadex* G-15. Yield: 860 mg (89 %); colourless/ slightly light-sensitive powder. ;! Characteriatinn •,;, 31£zH£m (109.3 MHz, D20/C2H5OH, -30 0C) : S= 8.9 ppm (dd) , [1J(107Ag,P) = 314 Hz; 1J(19Ag,P) = 350 Hz] IB (KBr, cm-1): v(SO) = 1224 (sh, vst) , 1198 (vst) < 1040 (vst), 622 (vst) Element analysis <C54H52AgNa8035P3S9; 1934.23) Calc. C 33.53 H 2.71 Ag 5.58 O 28.95 P 4.80 S 14.92 Pound C 33.15 H 2.76 Ag 5.70 O 28.98 P 4.79 S 14.09 Example 31: Synthesis of Au2 (TPPTS)2 [.u-PtC-m- S03Na)2(C6H4-m-S03)]2 • 8H20 150 mg (0.44 mmol) of tetrachlorogold(III) acid are dissolved in 5 ml of water saturated with nitrogen. A few seconds after the addition of 500 mg (0.80 mmol) of TPPTS the solution begins to lose colour. After 2-3 minutes it is colourless. After 4 hours of stirring, the water is removed in a vacuum and the residue dried in a vacuum (0.01 Torr corresponding to 1.33 Pa) Yield: 382 mg (31 %); colourless brittle glass. CharacberizaMnn 31£zJM£ (109.3 MHz, D20, 5 0C) : /= 43.23 ppm (broad signal) Element lysis (c72H68Au2Na10P4o46s12; 2801.7) Cale. C 30.87 H 2.45 Au 14.06 P 4.42 S 13.73 Found C 30.40 H 3.00 Au 12.90 P 3.06 S 11.90 40- Example 32: Synthesis of Au2 (TPPTSK [.u-PtCgH.-m- S03Na)2(C6H4-m-S03)]2 . 16 H20 0.52 g (2 mmol) of carbonyl chlorogoldr (CO)AuClr are dissolved in 20 ml of toluene. As soon as 3.52g (G mmol) of TPPTS in 10 ml of water are addedr a flaky white precipitate is formed. Stirring is performed for hours at room température, during which the pre¬ cipitate dissolves. After the phases have separated, the organic phase is v/ashed twice, in each case with ml of water. The combined aqueous phases are filtered and evaporated in a vacuum until dry. The raw product is purified by column chromatography on Fractogel TSK HW-40 or Sephadex*G-15. Yield: 1.08 g (54 %, related to TPPTS); pale-yellow powder. CharaçtenaaUim 3:L£ME (109.3 MHz, D20, 5 «O : cf- 41.7 ppm (s) . IB (KBr, cm"1): v(SO) = 1226 (sh, vst) , 1201 (vst), 1041 (vst), 623 (vst). Element analysis ogHAUjjNaOPgSj 4046.66) Calc. C 32.06 H 2.59 Au 9.73 Cl 0.0 O 27.63 P 4.59 S 14.26 Found C 30.96 H 2.46 Au 10.40 Cl 0.0 0 26.40 P 4.14 S 14.87 Example 33: Synthesis of Au9S(TPPTS)0 «6 Ho0 Variant A», 90 mg (0.28 mmol) of chloro(tetrahydroth.io- phene)gold(I) are dissolved in methylene chloride. A solution of 120 mg (0.23 mmol) of TPPTS in 10 ml of water is added to this solution to form a lower layer and the two-phase system is stirred intensively for hours. Then the water phase is separated and evapor¬ ated in a vacuum until dry. Yield: 70 mg (15 %). Variant B. A solution of 200 mg (0.07 mraol) of the compound from example 31 in 3 ml of ethanol-water (3+1 parts by volume) is cooled to 0 0C. On addition of 0.5 ml of a sodium sulfide solution saturated with nit- rogen (7.5 % ; 0.12 mmol) a white milkiness occurs which disappears again on addition of approx. 1 ml of water. The solvent is removed and the residue is dried in an oil-pump vacuum. Yield: 39 mg (33 %); yellow powder, which turns brown when it is stored for longer periods at room temperature (formation of gold sul¬ fide) . The product is purified by column chromato¬ graphy on Sephadex*G-25 under the exclusion of light. Characterization 31P-mR (109.3 MHz/ D20, 5 eC) : /= 31.76 ppm Slenient analysis (c36H36Au2Na6024p2s7; 1670*5) Calc. C 25.80 H 2.10 Au 23.50 P 3.70 S 13.40 Found C 24.30 H 2.20 Au 23.00 P 3.00 S 12.90 The following examples 34 to 56 describe the use of the new compounds as catalysts. Example 34: Catalytic hydrogénation of cyclohexene in the presence of Co2(CO)6(TPPTS)2 . 6 H20 as a catalyst 31 mg (0.02 mmol) of Co2(CO)6(TPPTS)2. 6 H-Or dis¬ solved in 2 ml of water/ as well as 820 mg (10 mmol) of freshly distilled cyclohexene are placed in a 100 ml laboratory autoclave under an argon atmosphere. The mixture is left to react for 20 hours at a hydrogen pressure of 3.0 MPa and 20 0C and then the phases are separated. According to a GC/MS analysis the organic phase consists of 7 % cyclohexane and 93 % cyclo- hexene. 42- .JE Example 35: Selective hydrogénation of 1-decene under hydroformylation conditions in the presence of C02(CO)g(TPPTS)2 • 6 HjO as a catalyst A solution of 31 mg (0.02 mmol) of Coj(CO)>(TPPTS)- "6 H20 in 2 ml of water and 0.70 g (5 mmol) bf 1-decene is placed in a 50 ml laboratory autoclave which has been rinsed for 15 mins with nitrogen. Then the mixture is left to react for 16 hours at 100 "C and a pressure of 7.0 MPa H/CO (1:1). After cooling to 25 0C the organic phase is extracted with 2 ml of methylene chloride. The GC/MS analysis shows 76 % n- decane and 24 % unchanged 1-decene. A corresponding aldehyde cannot be detected. Example 36: Catalytic hydrogénation of cyclohexene and cis-cyclooctene in the presence of Rh(NO)(TPPTS)3• 9 HjO as a catalyst a) Hydrogénation of cyclohexene without a solvent: mg of Rh(NO)(TPPTS)3• 9 H20 (0.01 mmol) in 1.5 ml of distilled water are placed in hydrogénation appar- atus to Marhan. 330 mg (4 mmol) of cyclohexene are added to this solution» the apparatus is rinsed with H, and left to react at 25 "C and 0.1 MPa H2 pressure for 92 hours. The organic phase is taken up with 3 ml of methylene chloride and dried over water-free sodium sulfate. According to GC/MS analysis the product con¬ sists of 63.3 % cyclohexane and 36.7 % cyclohexene. b) Hydrogénation of cyclohexene in solution: 40 mg (0.02 mmol) of Rh(NO)(TPPTS)3 • 9 H20 in a mixture of 3 ml of water and 3 ml of isopropanol are placed in hydrogénation apparatus to Marhan. 410 mg (5 mmol) of cyclohexene are added to this solutiorw the apparatus is rinsed briefly with H? and left to react at 25 0C and 0.1 MPa H2 pressure for 120 hours. The organic phase is taken up with 3 ml of methylene chloride and dried over water-free Na2S04. According to GC/MS an¬ alysis the product consists of 47 % cyclohexane and 5 3 % cyclohexene. c) Hydrogénation of cyclooctene under normal pressure; 100 g (0.05 mmol) of Rh(NO)(TPPTS), • 9 HjO in 5 ml of water are placed in hydrogénation apparatus to Marhan under an H2 atmosphere (0.1 MPa). Then 2.20 g (20 mmol) of freshly distilled cis-cyclooctene are added and the resultant two-phase mixture is stirred for 43 hours at 250C. The GC/MS analysis of the organic phase shows a cyclooctane/cyclooctene ratio of 30 : 70. After the experiment has run for 150 hours the cyclo- octane/cyclooctene ratio is 98 : 2. Example 37: Catalytic hydrogénation of cis-cyclooctene with IrCl((i,-lf5-C8H12) (TPPTS)2 • 6 H20 as a catalyst 2.75 g (25 mmol) of cis-cyclooctene and 79 mg (0.05 mmol) of (rç,4-lr5-C8H12)IrCl(TPPTS)2 • 6 H20 in 3 ml of water are placed in a 50 ml laboratory autoclave. After the autoclave has been rinsed twice with hydrogène II2 is injected until a pressure of 2.5 MPa is reached* then the mixture is heated for 20 hours to 100oC. The pressure rises to 3 MPa. After cooling to room temper- aturer the phases are separated. The GC/MS analysis of the organic phase shows that 64 % cyclooctane and 36 % cis-cyclooctene are present in the reaction product. Example 30: Catalytic reduction of nitrobenzene v'.'.irb carbon monoxide in the presence of Fe-TPPTS complex compounds as catalysts a) 470 mg (1.29 mmol) of Fe2 (CO) j, are boiled with a solution of 587 mg (1.29 mmol) of TPPTS in 50 ml of water for t, . Then 10 ml of nitrobenzene with 3 ml of ethanol are added and the mixture is boiled for another t2 [mini (cf. table 1) with reflux and CO-feed (0.1 MPa). After cooling the phases are separated. The nitrobenzene phase is freed from finely distributed iron hydroxide by passing it through a dense filter and then shaken with 1 % hydrochloric acid. This ex¬ tract is evaporated and the yield of aniline is deter¬ mined. In additionr before shaking with 1% hydro- chloric acid a sample of the nitrobenzene is taken for GC/MS analysis. The results are compiled in table 1. The red complex Fe4(CO)11(TPPTS) can be isolated from these preparations as a catalytically active compound and is then purified by gel chromatography on Sephadex* G-15. For this purpose the following procedure is adopted: The aqueous filtrate is concentrated to 30 ml in a vacuum. In order to isolate the catalytically active complex/ 40 g of Sephadex*G-15 in a 25-30 cm thick layer are applied to a glass sinter which is roughly 4 cm in diameter. The filtrate is added in the fast stream and two yellow fractions are extracted; they contain the complexes Fe(CO) . (TPPTS) and Fe(CO).,- (TPPTS)2 (cf. example 2). Then a brown zone is eluted at a flow rate of 1 drop/sec with pure water until the last remaining deep-redr extremely slow-moving zone has reached the end of the column. A red/ intensively colored, complex is extracted with water/ethanol (ratio 3:lr total 50 ml; then ratio 1:1) until the gel is only slightly pink in colour. At least 750 ml of . eluent are required. After the solvent has been re- moved in a vacuumr 110 mg of theùnew complex remain (2 wt. %f related to the Fe2(C0)Q used). Characteriaation 31P-NMR (109.3 MHzr DjO +5 0C): cf = 84.81 ppm. IE CKBr/ cm-1]: 2052 nw 2002 w, sh, 1963 w, 1900- 1835 (numerous shoulders). Elément analysis (c29H18Fe4Na3o23PS3; 1153.92) Calc. C 30.19 H 1.57 Fe 19.36 P 2.68 Found C 30.00 H 1.40 Fe 19.00 P 2.40 Table 1: Hydrogénation of nitrobenzene t] t? Pressure Molar ratio *) An iline HC1 (rain) (min) (MPa) (GC/MS-determination) (mg) *) Aniline/Nitrobenzene b) 45 mg (0.13 mmol) of Fe3(CC»12 are boiled for 1 hour with 175 mg (0.28 mmol) of TPPTS in 7 ml of water and 3 ml of ethanol with reflux/ a black powder pre- cipitating. The yellow filtered solution is mixed with 3 ml of 10 % KOH and 10 ml of nitrobenzene. Whilst CO is fed in/ the mixture is boiled for another 2 hours with reflux. After phase separation the nitrobenzene » phase is treated as described under a). as solvent/ plate not saturated): Rf = 0.49 lanilinelr Rf = 0.87/ Rf = 0.30. Example 39: Catalytic reduction of nitrobenzene with CO in the presence of COjtCO),(TPPTS)2 • 6 H-O as a catalyst 62 mg (0.04 mmol) of Co2(CO),(TPPTS), • 6 H20 in 5 ml of water and 490 mg (4 mmol) of nitrobenzene are placed in a 100 ml laboratory autoclave/ which has previously been rinsed for 15 min with nitrogen. (a) The mixture is stirred for 12 hours at 100 0C and 4.0 MPa CO pressure and the organic phase is then extracted with 5 ml of methylene chloride. The GC/MS analysis shows 4 % aniline and 96 % nitro¬ benzene. (b) The same procedure is adopted as in (a)/ but the mixture is stirred for 40 hours at 140 "C and 2.5 MPa CO pressure. Result (GC/MS analysis): 16.4 % aniline/ 83.6 % nitrobenzene. (c) The same procedure is adopted as in (a)/ but the mixture is stirred for 40 hours at 140 "C und 5.5 MPa CO pressure. Result (GC/MS analysis): 38.4 % aniline/ 61.6 % nitrobenzene. 47- Example 40: Hydrocarbonylation of ethylene with Co2(CO)6(TPPTS)2 . 6 H20 as a catalyst 153 mg (0.1 mmol) of Co2(CO)6(TPETS)2 . 6 H20 in 5 ml of water are placed in a 50 ml laboratory autoclave under a nitrogen atmosphere. Then ethylene is injected up to a pressure of 0.5 MPa (approx. 10 mmol) and CO up to a pressure of 4 MPa. The mixture is heated to 1450C and left to react for 40 hours at this temperature. After cooling to room temperature 2 ml of methylene chloride are added and the organic phase is examined using GC/MS analysis; apart from methylene chloride only diethyl- ketone [v(C0) = 1729 cm-1] . conversion is approx. 10 %. ketone [v(C0) = 1729 cm ] can still be detected. The Example 41: Hydroformylation of 1-hexene in the presence of Co2(CO)5(TPPTS)2 • 6 H20 as a catalyst 1.) 62 mg (0.04 mmol) of Co2(CO)6(TPPTS)2. 6 H20 and 0.45 g (0.08 mmol) of TPPTS in 3 ml of water are placed in a 50 ml laboratory autoclave under a nitrogen atmosphere. 1.62 g (20 mmol) of 1-hexene are added and C0/H2 is injected up to a pressure of 7 MPa. The mix¬ ture is heated to 110 "C and left to react for 18 hours at this temperature. After cooling to room temperaturer the phases are separated. The GC/MS analysis of the organic phase shows that the conversion of 1-hexene to heptanal(l) is 36 %f with an n/i ratio of 3.4 : 1. 2.) The aqueous phase is again mixed with 1.62 g (20 mmol) of 1-hexene. Hydroformylation is repeated under the same conditions as in 1. The GC/MS analysis of the organic phase shows that the conversion of 1-hexene to heptanal(l) is 35 %r with an n/i ratio of 2.1 : 1. 3.) 153 mg (0.01 mmol) of Co2(CO)6(TPPTS)2 • 6 H20 in ml of water are placed in a 50 ml laboratory autoclave under a nitrogen atmosphere. 0.84 g (1 mmol) of 1- hexene are added and CO injected .to a pressure of 5.5 MPa. The two-phase mixture is heated to 170ÔC. After hours of reaction at this température? it is left to cool to room temperature and the phases are separated. The GC/MS analysis of the organic phase shows that the 1-hexene has been completely reacted to heptanal(l) with an n/i ratio of 1 : 1. Example 42: Hydroformylation of ethylene with RhCKCO) (TPPTS) 2 . 6 H20 as a catalyst under a CO atmosphere 141 mg (0.1 mmol) of RhCl(CO)(TPPTS)2 • 6 H20 dissolved in 3 ml of water are placed in a 50 ml laboratory autoclave under a nitrogen atmosphere. Then ethylene is injected up to a pressure of 0.5 MPa (approx. 10 mmol) and then CO up to a pressure of 3 MPa. The mixture is heated to 120 0C and left to react for 22 hours at this temperature. After cooling to 0 0C the organic phase is isolated. The GC/MS and GC/IR analyses show that 0.65 g (approx 20 %) of propanal [v(CO) = 1743 cm" ] have formed. Example 43: Hydroformylation of 1-hexene with RhCKCO) (TPPTS) 2 • 6 H20 as a catalyst under a CO atmosphere 70 mg (0.05 mmol) of RhCKCO) (TPPTS) 2 . 6 H20 in 3 ml of water are placed in a 50 ml laboratory autoclave under a nitrogen atmosphere. Then 0.84 g (10 mmol) of 1-hexene are added and CO injected up to a pressure of 4 MPa. The two-phase mixture is heated to 100"C. After 49- 18 hours of reaction at this temperature/ it is left to cool to room temperature and the organic phase is isolated. The GC/MS analysis shows that the conversion of 1-hexene to heptanal(l) is 92 % with an n/i-ratio of 76 : 24. ,' Example 44: Hydroformylation of 1-hexene in the presence of Rhg(CO)7(TPPTS)9 • 27 H20 as a catalyst 65 mg (0.01 mmol) of Rhg(CO)_(TPPTS)9 ♦ 27 H20 and 0.17 g (0.3 mmol) of TPPTS in 3 ml of water are placed in a 100 ml laboratory autoclave under a nitrogen atmosphere. After addition of 1.62 g (20 mmol) of 1- hexener CO/H2 is injected up to a pressure of 5 MPa and the two-phase system is heated with vigorous stirring for 18 hours to 105oC/ the pressure rising to 5.7 MPa. After the reaction has been completedr the phases are separated. The organic phase is examined using GC/MS analysis. The aqueous phase containing the catalyst is reused for hydroformylation of the same amount of 1- hexene under the above-mentioned conditions. a) The GC/MS analysis of the colourless organic phase shows 84 % conversion of 1-hexene to heptanal(l) with an n/i ratio of 95 : 5. b) The GC/MS analysis of the organic phase shows 78 % conversion of 1-hexene to heptanal(l) with an n/i- ratio of 94 : 6. c) The GC/MS- analysis of the organic phase shows 75 % conversion of 1-hexene to heptanal(l) with an n/i ratio of 90 : 10. d) The GC/MS analysis of the organic phase shows 74 % conversion of 1-hexene to heptanal(l) with an n/i ratio of 84 : 16. 50- Example 45: Hydroformylation of 1-hexene in the presence of IrH(CO)(TPPTS)3 . 9 H20 as a catalyst 63 rag (0.03 mmol) of IrH(CO) (TPPTS)- . 9 HO and 0.51 g (0.9 mmol) of TPPTS in 3 ml of water are placed in a ml laboratory autoclave under a nitrogen atmosphere. After the addition of 2.52 g (30 mmol) of 1-hexenef CO/H2 is injected up to a pressure of 5 MPa and the two-phase system is heated to 110 0C/ the pressure rising to 6.5 MPa. After 20 hours of reaction at this temperature/ it is left to cool to room temperature and the phases are separated. The GC/MS analysis of the organic phase shows that the conversion of 1-hexene to heptanal(l) is 15 %* with an n/i ratio of 93 : 7. Example 46: Hydroformylation of 1-hexene in the presence of (cis-Cl2)Pt(TPPTS)2 . 6 H20 as a catalyst mg (0.03 mmol) of cis-Cl2Pt(TPPTS)2 • 6 H20 in 2 ml of water are placed in a 50 ml laboratory autoclave under an N2 atmosphere. After the addition of 2.43 g (30 mmol) of 1-hexenef CO/H2 is injected at room temperature to a pressure of 7 MPa and the two-phase system is left to react for 18 hours at 100oCr the pressure rising to 8 MPa. After the reaction has been completed the reaction solution is left to cool to room temperature and the phases are separated. The GC/MS analysis of the colourless organic phase shows that 58 % of the 1-hexene has been hydroformylated to heptanaKDf with an n/i ratio of 2 : 1. The aqueous phase is again mixed with 2.43 g (30 mmol) of 1-hexene. The hydroformylation is performed under the same conditions; 62 % heptanal(l) (n/i ratio 2.2 : 1) is obtained. 51- Example 47: Hydroformylation of 1-hexene in the presence of (cis-Cl-JPt(TPPTS), • 6 H,0/SnClo as a catalyst * 22 A 50 ml laboratory autoclave is charged with 45 mg (0-03 mmolJ of cis-CljPt (TPPTS) 2" • "g B2Q and 7 mg (0.03 mmol) of SnCl2. 2 H20 in 2 ml of water. After aaaition of 2.43 g (30 mmol) of 1-hexene, CO/H2 is injected up to a pressure of 7 MPa. The mixture is heated to 100 "Cf the pressure rising to 8 MPa, and stirred for 18 hours at this temperature. After cooling to room tem¬ perature the phases are separated. The GC/MS analysis of the colourless organic phase shows that 1-hexene has been completely reacted to a mixture of 70 wt. % n- heptanal(l), 26 wt. % i-heptanal(l) and 4 wt. % n- heptanol(l). Example 48: Catalytic oxidation of cyclohexene with iodosylbenzene and RuCl2(TPPTS)2 • 6 H20 as a catalyst 82 mg (1 mmol) of cyclohexene and 30 mg (0.02 mmol) of RuCl2(TPPTS)2 • 6 H20 in 2 ml of water are added to a suspension of 0.33 g (1.5 mmol) of iodosylbenzene in ml of methylene chloride and stirred for 5 hours bet¬ ween 10 0C and 15 "C. The GC/MS and GC/IR analyses of the organic phase show that 70 % of the cyclohexene is oxidised to cyclohexene oxide. Example 49: Catalytic oxidation of 3-hexine with iodosylbenzene and RuCl2(TPPTS)2 • 6 H20 as a catalyst 82 mg (1 mmol) of 3-hexine and 15 mg (0.01 mmol) of RuCl2(TPPTS)2' 6 H20 in 2 ml of water are added to a suspension of 0.66 g (3 mmol) of iodosylbenzene in 5 ml' of methylene chloride. The mixture is stirred for 3 hours at room temperature and the phases then separ- ated. The GC/MS and GC/IR analyses of the organic phase show that 3-hexine is completely oxidised to hexane- 3.4-dione [v(CO) = 1721 cm-1] and in addition iodo- benzene can also still be detected. Example 50: Catalytic oxidation of diphenylacetylene with iodosylbenzene and RuCl., (TPPTS) '. 6 Ho0 asa catalyst 2 A solution of 180 mg (1.0 mmol) of diphenylacetylene in 2 ml of methylene chloride and a solution of 15 mg (0.01 mmol) of RuCl2(TPPTS)2 • 6 H20 in 2 ml of water. are added to a suspension of 660 mg (3 mmol) of iodo¬ sylbenzene in 4 ml of methylene chloride. The mixture is stirred for 2 hours at room temperature, the aqueous phase turns green. After separation of the phases the organic phase, which is now clear, is subjected to GC/MS and GC/IR analyses; these analyses show that diphenylacetylene is completely oxidised to diphenyl- glyoxal (benzil) [v(CO) = 1692 cm-1]; in addition iodobenzene can still be detected. The aqueous phase is again mixed with 180 mg (1 mmol) of diphenylacetylene and 660 mg (3 mmol) of iodosylbenzene in 6 ml of methylene chloride. After a further reaction period of 2 hours at room temperature the phases are separated, and the GC/MS analysis of the organic phase shows that diphenylacetylene is completely oxidised to benzil. Example 51: Catalytic oxidation of 1-phenylethanol(1) with RuCl2(TPPTS)2 . 6 H20 as a catalyst 0.12 g (1 mmol) of 1-phenylethanol(1) and 30 mg (0.02 mmol) of RuCl2(TPPTS)2. 6 H20 in 2 ml of water are added to a suspension of 0.33 g (1.5 mmol) of iodosyl¬ benzene in 5 ml of methylene chloride. The aqueous phase rapidly turns dark-green. The mixture is left to react for 3 hours at room temperature and then the organic phase isolated. The GC/MS and GC/IR analyses of the organic phase show that 1-phenylethanol(1) is com¬ pletely oxidised to acetophenone tv(C=0) = 1705 cm-1]. Example 52: Catalytic oxidation of cyclohexanol with RuCl2(TPPTS)2 • 6 H20 as a catalyst 100 mg (1 mmol) of cyclohexanol and 30 mg (0.02 mmol) of RuCl2(TPPTS)2. 6 ELO in 2 ml of water are added to a suspension of 0.3 3 mg (1.5 mmol) of iodosylbenzene in 5 ml of methylene chloride. The mixture is left to react for 3 hours at room temperature and the organic phase is isolated. The GC/MS analysis shows that cyclo¬ hexanol is completely oxidised to cyclohexanone. Example 53: Catalytic oxidation of 1-phenylethanol(1) with iodosylbenzene and PddPPTS), • 9 H20 as a catalyst 49 mg (4 mmol) of 1-phenylethanol(1) and 80 mg (0.04 mmol) of Pd(TPPTS)3« 9 HjO in 3 ml of water are added to a suspension of 1.32 g (6 mmol) of iodosylbenzene in ml of,methylene chloride and stirred for 15 hours at 2g room temperature. The GC/MS analysis of the organic phase shows that 35 % of the 1-phenylethanol(1) is oxidised to acetophenone. Example 54: Catalytic oxidation of triphenylphosphane with PdCTPPTS), . 9 HjO as a catalyst 1) 60 mg (0.03 mmol) of Pd(TPPTS)3 . 9 H20 in 4 ml of water are added to 2.62 g (10 mmol) of triphenylphos¬ phane in 15 ml of toluene and the resultant two-phase mixture is vigorously stirred for 90 minutes in the air at room temperature. Then the organic phase is iso- lated by phase separation and dried over anhydrous :o|q sodium sulfate. The solvent is removed in a water-pump vacuum. The P-NMR spectrum shows that 86 % of the phosphane is oxidised to triphenylphosphane oxide. 2) 60 mg (0.03 mmol) of Pd(TPPTS)..* • 9 H20 in 4 ml of water are added to a solution of 2.62 g (10 mmol) of triphenylphosphane in 15 ml of toluene at room temper¬ ature and oxygen is passed through the resultant two- phase mixture for 90 minutes. The organic phase is isolated by phase separation and dried over anhydrous sodium sulfate. After the solvent has been removedr the residue is crystallised out of toluene. Yield: 2.77 g (99 %) 0=P(C(-HI.), ; colourless crystals. Characterization 31 P-NMR (109.3 MHzr C.,D0f 20 0C) : </"» 26.3 ppm (s) -1 ' ° IB (KBr, cm ): v(P=0) = 1187 (vst), 1117 (vst) Example 55: Catalytic carbon-carbon linking in the presence of Pd(TPPTS)3/CuI as a catalyst a) 40 mg (0.20 mmol) of copper(I)-iodide are stirred into a mixture of 10 ml of diethylaminef 1.78 g (11 mmol) of 3-ethyl-3-methyl-l-bromoallener 1.02 g (10 mmol) of phenylacetylene and 200 mg (0.1 mmol) of Pd(TPPTS)3 • 9 H20. After 15 hours of stirring at room temperature 3 ml of water are added and the diethyl- amine is removed in an oil-pump vacuum. The residue is extracted three times/ in each case with 30 ml of n- pentane and then washed three times/ in each case with ml of a saturated aqueous sodium chloride solution. After drying over anhydrous sodium sulfate the solvent is removed in a vacuum. The product 2-ethyl-6-phenyl- hexadiene(2.3)-ine(5)/ CH3-C(C2H5)C=C=C(H) C=C(C6H5) , is purified by chromatography on silica gel (0.063 - 0.200 mm) petroleum ether-diethylether (50 : 1) or by distillation in a rotating bulb tube. Yield: 1.10 g (60 %f related to phenylacetylene)/ yellow oil. b) 30 mg (0.16 mmol) of copper(I)-iodide are stirred into a mixture of 200 mg of NaOH \£5 mrnoi) in 10 ml of water/ 680 mg (4.2 mmol) of 3-ethyl-3-methyi-l-bromo- allene, 400 mg (4.0 mmol) of phenylacetylene and 160 mg (0.08 mmol) of Pd(TPPTS)3« 9 H20. The mixture is stirred for 40 hours at room temperature and then extracted three times» in each case with 25 ml of n- "LQ pentane. The organic phase is washed three times/ in each case with 20 ml of saturated sodium chloride solution and dried over anhydrous sodium sulfate; then the solvent is removed in a vacuum. Yield after purif¬ ication: 100 mg (14 %/ related to phenylacetylene). Characterization 1H-NMR (270 MHz/ 25 0C/ CDCl3):cf= 1.03 ppm (t/ 3 H# 3J = 7.5 Hz) CH2CH3/dr= 1.75 ppm (d/ 3 H# 5J = 2.9 Hz) = C(CH3)/ S= 1.97 - 2.14 ppm (m/ 2H) CH2CH3/ </= 5.52 (sext. 1 H, 5J = 2.8 Hz) = C(H), / = 7.22 - 7.42 ppm (m, 5H) CgHg IE (Film/ cm 1): V(C=C) = 2207; v(C=C=C) = 1947 c) 30 mg (0.16 mmol) of copper(I)iodide are stirred into a mixture of 0.2 g (5 mmol) of sodium hydroxide and 0.16 g (0.08 mmol) of Pd(TPPTS)3' 9 H20 in 10 ml of water. Then 0.68 g (4.2 mmol) of 3-ethyl-3-methyl-l- bromoallene and 0.4 g (4 mmol) of phenylacetylene in ml of pentane are added. The mixture is stirred for hours at room temperature and the phases are separated. The aqueous phase is extracted twice/ in each case with 15 ml of pentane. The organic phase is washed three times/ in each case with 20 ml of sodium chloride solution and dried over anhydrous sodium sulfate. Then the solvent is removed in a vacuum. Yield after purifi¬ cation: 0.25 g (35 %/ related to phenylacetylene); yellow oil Characterieation 1H-NMR (270 MHz, 250C/ CDC13) :/= 1*03 ppm (t, 3H, 3J Hz) = CÎCH-îf cf= i'97 ~ 2'1 PP™ (m, 2H) 5. IE (Film, cm-1): v(C=C) = 2207f v(C=C=C) = 1947 Example 56: Amine addition to a carbon-carbon double bond A solution of 60 mg (0.04 mmol) of PtCl2(TPPTS)2 • 6 H20 in 3 ml of water/ 4.08 g (60 mmol) of isoprene and 2.93 g (40 mmol) of diethylamine are placed in a 50 ml laboratory autoclave/ which has been rinsed for minutes with nitrogen. Then the mixture is heated for 2 days to 80oC/ a pressure of 0.2-0.3 MPa is reached. After cooling to room temperature the phases are sep- arated and the organic phase is dried over anhydrous sodium sulfate. The GC/MS analysis shows l-(N/N-di- ethylamino)-3-methylbutene(2)/ (CH3)2C=CHCH2N(C2H5)- in 69 % yield [v(C=CH) = 1670 cm"1;cr(=CH= = 843 cm" ]. Furthermore 22 % 1-(N/N-diethylamino)-2-methyl- butene(2)/ CH3CH = C(CH3)-CH2N(C2H5)2/ in 22 % yield [v(C=CH) = 1653 cm"1; cf (=CH) = 823 cm"1] is also formed. THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE



[2]

The invention relates to novel complex compounds of elements from groups VII A, VIII A and I B of the Periodic Table with the trisodium salt of tris(m-sulphophenyl)phosphine as complex ligands, and to the use of these complex compounds as catalysts for hydrogenations, for the water gas reaction, for hydrocarbonylations, hydroformylations, oxidations, C-C linking reactions (e.g. allene/alkyne coupling) and addition reactions of secondary amines with C-C double bonds.



1. A complex compound comprising a central atom selected from the group consisting of elements of Groups IB, VIIA, and VIIIA of the IUPAC Periodic Table, said compound containing a trisodium salt of tris(m-sulfophenyl)- phosphine as a complex ligand, excluding a reaction product of bis(l,5cyclooctadiene)- nickel with said salt, said compound being of the formula LVv1Lx2My[P(C6H4-m-S03Na)3]2 wherein L1 and L2 are individually ligands which, in addition to said salt, are bound to said central atom, M is said central atom, w, x, y, and z are integers, w and x are 0 to 7y, y is 1 to 6, and z is < 4y.

2. The compound of claim 1 comprising a further ligand taken from the class consisting of H, CO, NO, PF3, H20, S, halogen, 7r-olefin ligandsand w- acetylene ligands.

3. The compound of claim 2 wherein said jr-aromatic ligand is cyclopentadienyl.

4. The compound of claim 2 wherin said Tr-olefin ligand is cyclooctadiene.

5. The compound of claim 2 wherein said w-acetylene ligand is diphenylaceteylene.

6. The compound of claim 1 wherein said central atom is manganese, iron, ruthenium, cobalt, rhodium, irridium, nickel, palladium, platinum, copper, silver, or gold.

7. The compound of claim 6 wherein said compound is taken from the class consisting of is £.-4" B jm: managanese compounds (n5-C5H5)Mn(CO)2P(C6H4-m-S03Na)3], (r?5-C5H5)Mn(CO)P(C6H4-m-S03Na)3]2, iron compounds Fe(CO)4[P(C5H4-m-S03Na)3], Fe(CO)3[P(C6H4-m- S03Na)3]2,Fe4(CO)11[P(C6H4-m-S03Na)3], ruthenium compounds Ru(NO)2[P(C6H4-m-S03Na)3]2, RuCl2[P(C6H4-m-S03Na)3]2, cobalt compounds C02(CO)6[P(C6H4-m-S03Na)3]2, CoH(CO)[P(C6H4-m-S03Na)3]3, CoHJPCQIVm-SCNa, Co2(CO)4(H5C6-CsC-C6C5)[P(C6H4-m-S03Na)3]2, rhodiumcompoundsRhCl[P(C6H4-m-S03Na)3]3,Rh(NO)[P(C6H4-m- S03Na)3]3, Rh(CH3COO)[P(C6H4-m-S03Na)3]3, Rh(CO)(OH)[P(C5H4-m-S03Na)3]2, Rh(CO)Cl[P(C6H4-m- S03Na)3]2, Rh(M-Cl)(CO)[P(C6H4-m-S03Na)3]2, Rh(OH)[P(C6H4-m-S03Na)3]3, Rh2[P(C6H4-m- S03Na)3]2[P(C6H4-m-S03Na)2(C6H4-m-S03)]2, Rh20*. Cl2)(r,4C8H12[P(C6H4-m-S03Na)3]2, Rh6(CO)7P(C6H4-m- S03Na)3]9, iridium compounds Ir(NO)[PC6H4-m-S03Na)3]3, IrCl(CO)[P(C6H4-m- S03Na)3]3, IrH(CO)P(C6H4-m-S03Na)3]3, Ir-COCrj4- C8H12)[P(C6H4-m-S03Na)3]2, nickel compounds Ni[P(C6H4-m-S03Na)3]3, Ni(CO)2[P(C6H4-m- S03Na)332)Ni(PF3)2[P(C6H4-m-S03Na)3]2, a palladium compound PdQFV-m-SCNak, platinum compounds Pt[P(C6H4-m-S03Na)3]4, PtCl2[P(C6H4-m- S03Na)3]2, hi a copper compound Cu3[P(C6H4-m-S03Na)3]2|>i-P(C6H4-m- S03Na)2(C6H4-m-S03)]3) a silver compound Ag[P(C6H4-m-S03Na)3]2[P(C6H4-m- SOaNaC-m-SOJ, and gold compounds Au2[P(C6H4S03Na)3]2(yx-P(C6H4-m-S03Na)2- (C6H4-m-S03)2, Au2[P(C6H4-m-S03Na)3]4[/i-P(C6H4-m- S03Na)2(C6H4-m-S03)]2,Au2S[P(C6H4-m-S03Na)3]2. (f0 jm: