Kuwata S, Kabashima S, Sugiyama N, Ishii Y, Hidai M
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
Inorg Chem. 2001 Apr 23;40(9):2034-40. doi: 10.1021/ic0009324.
Treatment of the hydrosulfido-bridged titanium-ruthenium heterobimetallic complex [Cp2Ti(mu2-SH)2RuCl(eta5-C5Me5)] (1; Cp = eta5-C5H5) with an excess of triethylamine followed by addition of [RuCl2(PPh3)3] and [[(cod)M]2(mu2-Cl)2] (M = Rh, Ir; cod = 1,5-cyclooctadiene) led to the formation of the TiRu2 and TiRuM mixed-metal sulfido clusters [(CpTi)[(eta5-C5Me5)Ru]Ru(PPh3)22(mu2-Cl)2] (3) and [(CpTi)[(eta5-C5Me5)Ru]M(cod)2(mu2-Cl)] (M = Rh (4a), Ir (4b)), respectively. On the other hand, the reactions of 1 with [M(PPh3)4] (M = Pd, Pt) afforded the TiRuM trinuclear clusters [(CpTiCl)[(eta5-C5Me5)Ru]M(PPh3)2(mu2-S)(mu2-H)] (M = Pd (5a), Pt (5b)) with an unprecedented M3(mu3-S)(mu2-S) core. The detailed structures of these triangular clusters 3-5 have been determined by X-ray crystallography. Crystal data: 3, triclinic, P1, a = 12.448(4) A, b = 12.773(4) A, c = 17.270(4) A, alpha = 100.16(2) degrees, beta = 99.93(2) degrees, gamma = 114.11(3) degrees, V = 2373(1) A(3), Z = 2; 4a, triclinic, P1, a = 7.714(2) A, b = 11.598(3) A, c = 14.802(4) A, alpha = 80.46(2) degrees, beta = 82.53(2) degrees, gamma = 71.47(2) degrees, V = 1234.0(6) A3, Z = 2; 4b, triclinic, P1, a = 7.729(1) A, b = 11.577(2) A, c = 14.766(3) A, alpha = 80.14(1) degrees, beta = 82.71(1) degrees, gamma = 71.55(1) degrees, V = 1231.1(4) A3, Z = 2; 5a, monoclinic, P2(1)/c, a = 11.259(4) A, b = 16.438(4) A, c = 26.092(5) A, beta = 102.23(3) degrees, V = 4719(2) A(3), Z = 4; 5b, monoclinic, P2(1)/n, a = 11.369(2) A, b = 16.207(3) A, c = 26.116(2) A, beta = 102.29(1) degrees, V = 4701(1) A3, Z = 4.
用过量三乙胺处理氢硫基桥连的钛 - 钌异双金属配合物[Cp2Ti(μ2 - SH)2RuCl(η5 - C5Me5)] (1; Cp = η5 - C5H5)，随后加入[RuCl2(PPh3)3]和[[(cod)M]2(μ2 - Cl)2] (M = Rh, Ir; cod = 1,5 - 环辛二烯)，分别得到了TiRu2和TiRuM混合金属硫簇[(CpTi)[(η5 - C5Me5)Ru][Ru(PPh3)2](μ3 - S)2(μ2 - Cl)2] (3)和[(CpTi)[(η5 - C5Me5)Ru][M(cod)](μ3 - S)2(μ2 - Cl)] (M = Rh (4a), Ir (4b))。另一方面，1与[M(PPh3)4] (M = Pd, Pt)的反应得到了具有前所未有的M3(μ3 - S)(μ2 - S)核的TiRuM三核簇[(CpTiCl)[(η5 - C5Me5)Ru][M(PPh3)2](μ3 - S)(μ2 - S)(μ2 - H)] (M = Pd (5a), Pt (5b))。这些三角形簇3 - 5的详细结构已通过X射线晶体学确定。晶体数据：3，三斜晶系，P1，a = 12.448(4) Å，b = 12.773(4) Å，c = 17.270(4) Å，α = 100.16(2)°，β = 99.93(2)°，γ = 114.11(3)°，V = 2373(1) Å3，Z = 2；4a，三斜晶系，P1，a = 7.714(2) Å，b = 11.598(3) Å，c = 14.802(4) Å，α = 80.46(2)°，β = 82.53(2)°，γ = 71.47(2)°，V = 1234.0(6) Å3，Z = 2；4b，三斜晶系，P1，a = 7.729(1) Å，b = 11.577(2) Å，c = 14.766(3) Å，α = 80.14(1)°，β = 82.71(1)°，γ = 71.55(1)°，V = 1231.1(4) Å3，Z = 2；5a，单斜晶系，P2(1)/c，a = 11.259(4) Å，b = 16.438(4) Å，c = 26.092(5) Å，β = 102.23(3)°，V = 4719(2) Å3，Z = 4；5b，单斜晶系，P2(1)/n，a = 11.369(2) Å，b = 16.207(3) Å，c = 26.116(2) Å，β = 102.29(1)°，V = 4701(1) Å3，Z = 4。
