Rhodium dicarbonyl chloride dimer, [Rh(C0)2C1]2, reacts with cis-and trans-8-styryldiphenylarsine, cis-o-styryldiphenylphosphine, bis(1-propynyl)phenylphosphine, and tris(ferroceny1)phosphine to give complexes of the type [Rh(CO)ClL2] (L = phosphine or arsine). Using an excess of cis-1,2-bis(diphenylphosphino)ethylene or bis (diphenylphosphinomethy1) ether, ionic complexes of the type [Rh(L-L)2]X (L-L = diphosphine, X = anion) are obtained. Polymeric complexes of formula [Rh(C0)C1(L-L)ln (L-L = diphosphine) result from the reaction with trans-1,2-bis(dipheny1phosphino)ethylene and bis(dipheny1phosphino)acetylene. By contrast, complexes of the same empirical formula prepared from bis(dipheny1-phosphin0)methane and its arsenic analog are dimers. When used in a 2 : 1 molar ratio, cis-1,2-bis(diphenylphosphino)ethylene and [Rh(CO)&l]z give [Rh(L-L)e] [Rh(C0)2C12] (L-L = diphosphine). An analogous reaction with the arsenic analog gives [Rh(CO)(L-L)z] [Rh(C0)2C12] (L-L = diarsine).Conductance and infrared spectral data are presented and the structures of the complexes are discussed.A number of bromo analogs were also prepared.
A variety of di(tertiary phosphines and arsines) (Lz) react with "RuC13*3HzO" in ethanol to produce the Ru(I1) complexes trans-[Ru(Lz)zCl~]. When LZ is bis(diphenylarsino)methane, [Ru(Lz)3Clz] is obtained in which both mono-and bidentate diarsine ligands are present. This complex reacts with carbon monoxide to produce [Ru(Lz)z(C0)2Clz] which contains only monodentate ligands. The same species results when this ligand is reacted with the mixture of ruthenium carbonyl complexes produced by reductive carbonylation of "RuC13*3H~0" in ethanol. The same procedure using the ligands bis(dipheny1phosphino)methane and cis-1,2-bis(diphenylarsino)ethylene produces Ru (L2)(CO)ZClz. Reaction of trans-[Ru-(DPM)zClz] (DPM = bis(dipheny1phosphino)methane) with carbon monoxide gives a cationic complex, trans-[ R U ( D P M )~-(CO)Cl]Cl. This complex reacts further with NO or alkyl nitrites to produce [Ru(NO)Cl(DPM)z] (BF4)z. With the mixture of ruthenium carbonyl complexes, trans-8-styryldiphenylphosphine or -arsine (L) initially give mer-[RuLB(CO)C~Z] which react further with carbon monoxide to give cis-[RU(CO)~LZCL]. Similar reactions using cis-8-styryldiphenylphosphine or -arsine give only cis-[RuLz(CO)&l~]. A number of other nitrosyl complexes [Ru(NO)(L2)C13] could be prepared starting from Ru-(NO)& Attempts to reduce the Ru(I1) complexes to Ru(0) species were generally unsuccessful. [Ru(DPM)zC~Z] also reacts with NOBFa to produce initially the Ru(II1) complex [ R U ( D P M ) Z C~~] B F~.The nmr and infrared spectra of the complexes are discussed.
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