Reactions between Ru3(μ-H)(μ3-SBut)(CO)9 and dppm have given Ru3(μ-H)(μn- SBut)(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 Rw were 0.036 and 0.038, respectively, for 4729 reflections with I ≥ 3.0σ(I).
High-nuclearity ruthenium carbonyl cluster chemistry. 9. Ligand substitution at decaruthenium carbonyl clusters