title: Formation of a Stable Complex, RuCl2(S2CPPh3)(PPh3)2, Containing an Unstable Zwitterion from the Reaction of RuCl2(PPh3)3 with Carbon Disulfide.
abstract: New insight into the complexity of the reaction of the prominent catalyst RuCl2(PPh3)3 with carbon disulfide has been obtained from a combination of X-ray diffraction and (31)P NMR studies. The red-violet compound originally formulated as a cationic π-CS2 complex, [RuCl(π-CS2)(PPh3)3]Cl, has been identified as a neutral molecule, RuCl2(S2CPPh3)(PPh3)2, which contains the unstable zwitterion S2CPPh3. In the absence of RuCl2(PPh3)3, there is no sign of a reaction between triphenylphosphine and carbon disulfide, although more basic trialkylphosphines form red adducts, S2CPR3. Despite the presence of an unstable ligand, RuCl2(S2CPPh3)(PPh3)2 is remarkably stable. It survives melting at 173-174 °C intact, is stable to air, and undergoes reversible electrochemical oxidation to form a monocation. When the reaction of RuCl2(PPh3)3 with carbon disulfide is conducted in the presence of methanol, crystals of orange [RuCl(S2CPPh3)(CS)(PPh3)2]Cl·2MeOH and yellow RuCl2(CS)(MeOH)(PPh3)2 also form. (31)P NMR studies indicate that the unsymmetrical dinuclear complex (SC)(Ph3P)2Ru(μ-Cl)3Ru(PPh3)2Cl is the initial product of the reaction of RuCl2(PPh3)3 with carbon disulfide. A path connecting the isolated products is presented.
authors: Department of Chemistry, University of California, 1 Shields Avenue, Davis, California 95616, United States.
authors: Kamran B
authors: KB
authors: Ghiassi
authors: Department of Chemistry, University of California, 1 Shields Avenue, Davis, California 95616, United States.
authors: Daniel T
authors: DT
authors: Walters
authors: Department of Chemistry, University of California, 1 Shields Avenue, Davis, California 95616, United States.
authors: Michael M
authors: MM
authors: Aristov
authors: Department of Chemistry, University of California, 1 Shields Avenue, Davis, California 95616, United States.
authors: Natalia D
authors: ND
authors: Loewen
authors: Department of Chemistry, University of California, 1 Shields Avenue, Davis, California 95616, United States.
authors: Louise A
authors: LA
authors: Berben
authors: Department of Chemistry, University of California, 1 Shields Avenue, Davis, California 95616, United States.
authors: Melissa
authors: M
authors: Rivera
authors: Department of Chemistry, University of California, 1 Shields Avenue, Davis, California 95616, United States.
authors: Marilyn M
authors: MM
authors: Olmstead
authors: Department of Chemistry, University of California, 1 Shields Avenue, Davis, California 95616, United States.
authors: Alan L
authors: AL
authors: Balch