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Novel dppm-ligated ruthenium-tin clusters have been prepared from the reaction of [Ru3(CO)10(µ-dppm)] with Ph3SnH. At room temperature and in the presence of Me3NO, [Ru3(CO)9(SnPh3)(µ-dppm)(µ-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 [Ru3(CO)7(SnPh3)2(µ-SnPh2)(µ-dppm)(µ-H)(µ3-H)] (2) which results from both Sn-H and Sn-C bond scission and contains two different hydride environments ( and 3) and a -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 o C liberates benzene to give [Ru3(CO)8(SnPh3)(µ-SnPh2)(µ3-SnPh2)(µ-dppm)(-H)] (3). DFT calculations confirm that the hydride bridges one of the Ru--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.2

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