Cluster Chemistry. XLIII. Sulfur-Carbon Bond Cleavage Reactions in the Hydrogenation of Some Sulfur-Containing Ruthenium Carbonyl Cluster Complexes: X-Ray Structure of Ru₃(μ-H)2(μ₃-S)(μ-(Z)-Ph₂PCH=CHPPH₂)(CO)₇

Abstract

Reactions between Ru₃(μ-H)(μ₃-SBu^t)(CO)₉ and dppm have given Ru₃(μ-H)(μ_n- SBu^t)(μ-dppm)(CO)_10-n(n = 2,3); hydrogenation of all three complexes resulted in S-C bond cleavage and formation of Ru₃(μ-H)₂(μ₃-S)(CO)₇(L₂) [L₂ = (CO)₂, μ-dppm]. Facile substitution of 2CO in Ru₃(μ-H)₂(μ₃-S)(CO)₉ by dppm, dpam or ebdp (L₂), catalysed by Na⁺[Ph₂CO]^- or [ppn][OAc], gave Ru₃(μ-H)₂(μ₃-S)(μ-L₂)(CO)₇, in which the bis-tertiary phosphine (or arsine) bridges an edge of the Ru₃ triangle, with the P (or As) atoms occupying equatorial positions. In the case of L₂ = ebdp, this edge is also bridged by H, as shown by a single-crystal X-ray structure determination. Crystals of the title compound are mcnoclinic, space group P2₁/n, with unit cell parameters a 13.454(3), b 17.748(2), c 14.706(2) Ǻ, and β 94.50(1)°. The structure was refined by a full-matrix least-squares method; at convergence R and R_w were 0.036 and 0.038, respectively, for 4729 reflections with I ≥ 3.0σ(I).