Silver, sulfoxide complexes

Other polydentate ligands are polyamines and related ligands. Stability constants of silver(I) complexes with polyamines in dimethyl sulfoxide,419 A-methyl-substituted 4-methyldiethylene-triamines,420 or ethylene- or N- or C-methylated ethylenediamine in aqueous solution have been reported.421 The structure of the silver 1,3-diaminopropane complex, [Ag NH2(CH2)3NH2 ]-C104,422 and complex formation with 1,4-diaminobutane and 1,5-diaminopentane have been reported.423 A dinuclear silver(I) compound with ethylenediamine [(enH)Ag(en)Ag(enH)2]4+ has... 

Diphenyl Tellurium Diperchlorate/Dimethyl Sulfoxide Complex A mixture of 0.70 g (2 mmol) diphenyl tellurium dichloride, 0.83 g (4 mmol) silver perchlorate and 30 ml dichloromethane is stirred at 20° for 1 h. The precipitated silver chloride is removed by filtration. The filtrate is mixed with a solution of 0.15 g (2 mmol) dimethyl sulfoxide in 10 ml dichloromethane. The mixture is refluxed for 5 h. The solvent is distilled from the mixture. The residue is treated with petroleum ether (40-60°). The resulting white solid is recrystallized from petroleum ether (40-60°)/dichloromethane (3 1) and then dried under reduced pressure 95% yield m.p. 140°. 

Complexes. Silver tetrafluoroborate is insoluble in cyclohexane but very soluble in water, ether, toluene, and nitromethane, and moderately soluble in benzene and cyclohexene. - Solubility in the unsaturated hydrocarbons is attributed to n-bond formation between the unsaturated compound and silver ion. Complexes have been observed with both ir-electron donors and lone-pair donors thus Meerwein prepared stable complexes with benzene, mesitylene, cycloheptatriene, diethyl ether, dimethyl sulfoxide, and a series of acid nitriles. However, the silver tetrafluoroborate-benzene complex is reported variously as a 1 1 complex, a 1 2 complex, and as a 2 3 complex. ... 

The technique of performing halide abstraction via interaction of a metal halo complex with a silver(I), thallium(I), or nitrosonium salt (see ref. 142, for discussion) has proved useful in the isolation of many novel sulfoxide complexes. Thus, [Pd(S-Me2S0)2(0-MejS0)j]-... 

Trilialophenols can be converted to poly(dihaloph.enylene oxide)s by a reaction that resembles radical-initiated displacement polymerization. In one procedure, either a copper or silver complex of the phenol is heated to produce a branched product (50). In another procedure, a catalytic quantity of an oxidizing agent and the dry sodium salt in dimethyl sulfoxide produces linear poly(2,6-dichloro-l,4-polyphenylene oxide) (51). The polymer can also be prepared by direct oxidation with a copper—amine catalyst, although branching in the ortho positions is indicated by chlorine analyses (52). 

Problems of dilution and pH sensitivity have also been encountered in the synthesis of cts-[Pt(S-R2SO)(olefin)Cl2] complexes (85), where deoxygenation of the sulfoxide with concomitant oxidation of the metal center occurs at low pH. The reactions of [M(Ph2PCH2CH2PPh2)Cl2] (M = Pd, Pt) with one equivalent of silver perchlorate in the presence of Me2SO yield either the O-Me O complex or its deoxygenation product, depending upon reaction conditions. A sequence of reactions, Eq. (27), has been proposed (143). 

Activation of carbon—hydrogen bonds in benzyl phenyl sulfoxides catalysed by palladium may lead to dibenzothiophene derivatives (39). lodoarenes and silver salts are required as additives, and product formation requires several consecutive catalytic cycles. The copper-catalysed conversion of bisaryloxime ethers to 2-arylbenzoxazoles is likely to involve complexation of the catalyst at... 

The initiator system, AgNOs-tetraethyllead, is used for the polsrmerization of VF in dimethyl snlfoxide (69). Dimethyl sulfoxide permits the pol3rmerization to proceed for longer periods than do other solvents by complexing of silver ions. 

R. E. Dodd and R. P. H. Gasser, Proc. Chem. Soc., 415 (1964). Complex formation in dimethyl sulfoxide. Heats of solution of mixtures of potassium cyanide with either silver (1) cyanide or copper (1) cyanide. 

There are many examples of the synthesis of homoleptic solvento-complexes by halide abstraction from compounds containing both coordinated halides and solvento-ligands. Palladium chloride is known to dissolve in nitriles, dimethylformamide, and dimethyl sulfoxide with the formation of complexes of the type [PdCl2(solv)2] which can be isolated as solids.3 The reaction of [PdCl2(RCN)2] with an excess of silver ions s is a convenient method for the synthesis of [Pd(RCN)4]2+. The tetra(acetonitrile)-platinum(II) and tetra(propionitrile)platinum(II) salts have been prepared in this way (Scheme 4.6). Wayland and Schramm have synthesized homoleptic palladium(II) complexes with DMSO, DMF, and DMAA in a similar manner. 

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