Synthesis of TiRu₂ 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 complex [Cp₂Ti(μ₂-SH)₂RuCl(η⁵-C₅Me₅)] (1; Cp = η⁵-C₅H₅) with an excess of triethylamine followed by addition of [RuCl₂(PPh₃)₃] and [{(cod)M}₂(μ₂-Cl)₂] (M = Rh, Ir; cod = 1,5-cyclooctadiene) led to the formation of the TiRu₂ and TiRuM mixed-metal sulfido clusters [(CpTi){(η⁵-C₅Me₅)Ru}{Ru(PPh₃)₂}(μ₃-S)₂(μ₂-Cl)₂] (3) and [(CpTi){(η⁵-C₅Me₅)Ru}{M(cod)}(μ₃-S)₂(μ₂-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){(η⁵-C₅Me₅)Ru}{M(PPh₃)₂}(μ₃-S)(μ₂-S)(μ₂-H)] (M = Pd (5a), Pt (5b)) with an unprecedented M₃(μ₃-S)(μ₂-S) core. The detailed structures of these triangular clusters 3−5 have been determined by X-ray crystallography. Crystal data:  3, triclinic, P1̄, 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) ų, Z = 2; 4a, triclinic, P1̄, 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) ų, Z = 2; 4b, triclinic, P1̄, 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) ų, Z = 2; 5a, monoclinic, P2₁/c, a = 11.259(4) Å, b = 16.438(4) Å, c = 26.092(5) Å, β = 102.23(3)°, V = 4719(2) ų, Z = 4; 5b, monoclinic, P2₁/n, a = 11.369(2) Å, b = 16.207(3) Å, c = 26.116(2) Å, β = 102.29(1)°, V = 4701(1) ų, Z = 4.