Syntheses and characterization of diruthenium(III) alkyl-alkyl and alkyl-alkynyl complexes with two bridging thiolate ligands *RuR(μ-SPri)2RuCp*R'> (Cp* = η5-C5Me5). X-ray structure of *Ru(CH2CH2Ph)(μ-SPri)2RuCp*(CH2CH2Ph)>

Article abstract of DOI:10.1016/0022-328X(95)05477-7

Reactions of diruthenium alkyl-halido complexes containing two bridging thiolate ligands *RuR(μ-SPrⁱ)2RuCp^*X> (1; Cp^* = η⁵-C5Me5, R = PhCH2CH2, X = Br, R = Me, X = I) with R'MgX (R' = PhCH2CH2, X = Br; R' = PhCH2, X = Cl) or R'Li (R' = Me, PhC<*>C) in THF at room temperature afforded novel diruthenium alkyl-alkyl and alkyl-alkynyl complexes *RuR(μ-SPrⁱ)2RuCp^*R'> (2).In contrast, treatment of 1a (R = PhCH2CH2, X = Br) with EtMgBr resulted in the formation of an alkyl-hydrido complex *Ru(CH2CH2Ph)(μ-SPrⁱ)2RuCP^*H) as the only isolableproduct.X-ray analysis of 2a (R = R' = PhCH2CH2) has disclosed the structure as consisting of the two Cp^*Ru(CH2CH2Ph) units connected by two μ-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 P2₁/c (No. 14) with a = 19.449(3) Angstroem, b = 10.210(3) Angstroem, c = 20.254(2) Angstroem, β = 94.684(9) deg, V = 4008(2) Angstroem³, Z = 4, and R(R_w) = 0.054 (0.041) for 2635 reflections 3?(I)>.Treatment of 2a with two equivalents of I2 in THF resulted in the formation of PhCH2CH2I and *RuI(μ-SPrⁱ)2RuCp^*I> (7c) as the major products, while treatment with 1.2 equivalents of I2 afforded a mixture of Ph(CH2)4Ph and PhCH2CH2I along with 7c and unidentified species. Keywords: Ruthenium; Thiolate; Alkyl; X-ray structure