SYNTHESES AND CHARACTERIZATION OF DIRUTHENIUM(III) ALKYL-ALKYL AND ALKYL-ALKYNYL COMPLEXES WITH 2 BRIDGING THIOLATE LIGANDS [CP-ASTERISK-RUR(MU-SPRI)(2)RUCP-ASTERISK-R'](CP-ASTERISK=ETA(5)-C(5)ME(5)) - X-RAY STRUCTURE OF [CP-ASTERISK-RU(CH(2)CH(2)PH)(MU-SPRI)(2)RUCP-ASTERISK(CH(2)CH(2)PH)]

Reactions of diruthenium alkyl-halido complexes containing two bridging thiolate ligands [Cp*RuR(mu-SPri)(2)RuCp*X](1; Cp* = eta(5)-C(5)Me(5), R = PhCH(2)CH(2), X = Br, R = Me, X = I) with R'MgX(R' = PhCH(2)CH(2), X = Br; R' = PhCH(2), X = Cl) or R'Li(R'= Me, PhC = C) in THF at room temperature afforded novel diruthenium alkyl-alkyl and alkyl-alkynyl complexes [Cp*RuR(mu-SPri)(2)RuCp*R'] (2). In contrast, treatment of 1a (R = PhCH(2)CH(2), X = Br) with EtMgBr resulted in the formation of an alkyl-hydrido complex [Cp*Ru(CH(2)CH(2)Ph)(mu-SPri)(2)RuCp*H] as the only isolable product. X-ray analysis of 2a (R = R'= PhCH(2)CH(2)) has disclosed the structure as consisting of the two Cp*Ru(CH(2)CH(2)Ph) units connected by two mu-SPri ligands together with a Ru-Ru single bond, in which the two alkyl groups are oriented mutually cis. Crystal data for 2a: monoclinic, space group P2(1)/c(No. 14) with a = 19.449(3) Angstrom, b = 10.210(3) Angstrom, c = 20.254(2) Angstrom, beta = 94.684(9)degrees, V = 4008(2) Angstrom(3), Z = 4, and R(R(W)) = 0.054 (0.041) for 2635 reflections [I > 3 sigma(I)]. Treatment of 2a with two equivalents of I-2 in THF resulted in the formation of PhCH(2)CH(2)I and [Cp*RuI(mu-SPri)(2)RuCp*I] (7c) as the major products, while treatment with 1.2 equivalents of I-2 afforded a mixture of Ph(CH2)(4)Ph and PhCH(2)CH(2)I along with 7e and unidentified Ru species.