Synthesis of TiBu2 heterobimetallic and TiRuM (M = Rh, Ir, Pd, Pt) heterotrimetallic sulfido clusters from a hydrosulfido-bridged titanium-ruthenium complex

Treatment of the hydrosulfido-bridged titanium-ruthenium heterobimetallic c omplex [Cp2Ti(mu (2)-SH)(2)RuCl(eta (5)-C5Me5)] (1; Cp = eta (5)-C5H5) with an excess of triethylamine followed by addition of [RuCl2(PPh3)(3)] and [{ (cod)M}(2)- (mu (2)-Cl)(2)] (M = Rh, Ir; cod = 1,5-cyclooctadiene) led to t he formation of the TiRu2 and TiRuM mixed-metal sulfido clusters [(CpTi){(e ta (5)-C5H5)Ru}{Ru(PPh3)(2)}(mu (3)-S)(2)(mu (2)-Cl)(2)] (3) and [(CpTi){(e ta (5)-C5Me5)Ru}{M(cod)}-(mu (3)-S)(2)(mu (2)-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){(eta (5)-C5Me5)Ru} {M(PPh3)(2)}(mu (3)-S)(mu (2)-S)(mu (2)-H)] (M = Pd (5a), Pt (5b)) with an unprecendent M-3(mu (3)-S)(mu (2)-S) core. The detailed structures of these triangular clusters 3-5 have been determined by X-ray crystallograph. Crys tal data: 3, triclinic, P (1) over bar, a = 12.448(4) Angstrom, b = 12.773- (4) Angstrom, c = 17.270(4) Angstrom, alpha = 100.16(2)degrees, beta = 99.9 3(2)degrees, gamma = 114.11(3)degrees, V = 2373(1) Angstrom (3), Z = 2; 4a, triclinic, P (1) over bar, a = 7.714(2) Angstrom, b = 11.598(3) Angstrom, c = 14.802(4) Angstrom, alpha = 80.46(2)degrees, beta = 82.53(2)degrees, ga mma = 71.47(2)degrees, V = 1234.0(6) Angstrom (3), Z = 2; 4b, triclinic, P (1) over bar, a = 7.729(1) Angstrom, b = 11.577(2) Angstrom, c = 14.766(3) Angstrom, alpha = 80.14(1)degrees, beta = 82.71(1)degrees, gamma = 71.55(1) degrees, V = 1231.1(4) Angstrom (3), Z = 2; 5a, monoclinic, P2(1)/c, a = 11 .369(2) Angstrom, b = 16.207(3) Angstrom. c = 26.116(2) Angstrom, beta = 10 2.29(1)degrees, V = 4701(1) Angstrom (3), Z = 4.