Mixed main group transition metal clusters: Reactions of [Ru3(CO)10(μ-dppm)] with Ph3SnH

Novel dppm-ligated ruthenium-tin clusters have been prepared from the reaction of [Ru-3(CO)(10)(mu-dppm)] with Ph3SnH. At room temperature and in the presence of Me3NO, [Ru-3(CO)(9)(SnPh3) (mu-dppm) (mu-H)] (1) is produced from the formal loss of CO and Sn-H bond oxidative-addition. Treatment of 1 with a further two equivalents of Ph3SnH (in the presence of Me3NO) gave [Ru-3(CO)(7)(SnPh3)(2)(mu-SnPh2)(mdppm)( mu-H)(mu(3)-H)] (2) which results from both SneH and SneC bond scission and contains two different hydride environments (m and mu(3)) and a mu-SnPh2 moiety. Cluster 2 has 48 CVE (cluster valence electron) with three formal ruthenium-ruthenium bonds; two of those are very long and fall at the extreme end of distances attributed to ruthenium-ruthenium bonds. Thermolysis of 2 at 66 degrees C liberates benzene to give [Ru3(CO) 8(SnPh3)(mu-SnPh2)(mu(3)-SnPh2)(mu-dppm)(mu-H)] (3). DFT calculations confirm that the hydride bridges one of the Ru-mu-SnPh2 bonds in 3. The solid-state structures of 2 and 3 have been determined by X-ray crystallography, and the bonding and ligand distribution have been investigated by DFT studies. The geometry-optimized structures are consistent with the solid-state structures. (C) 2017 Elsevier B.V. All rights reserved.