Reactivity of Ph<sub>2</sub>P(Se)CH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>CH<sub>2</sub>P(Se)Ph<sub>2</sub> with [M<sub>3</sub>(CO)<sub>12</sub>] (M = Ru or Fe). Synthesis and Characterization of the New Carbene Cluster [Ru<sub>3</sub>(μ<sub>3</sub>-Se)(μ<sub>3</sub>-H)(μ<sub>2</sub>-PPh<sub>2</sub>)(CO)<sub>6</sub>(μ<sub>2</sub>-CHC<sub>6</sub>H<sub>4</sub>CH<sub>2</sub>PPh<sub>2</sub>)]
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The reactions of [M3(CO)12] (M = Ru or Fe) with 1,2 bis[(diphenylphosphino)methyl]benzene diselenide (dpmbSe2) in hot toluene afford a variety of phosphine-substituted selenido carbonyl clusters. They belong to the following three families: (i) 50-electron clusters with a M3Se2 core (2, 3, 5−7), (ii) 48-electron clusters with a M3Se core (1, 8), (iii) 34-electron clusters with a M2Se2 core (4). All these species derive from the PSe bond cleavage. Cluster 1, which contains a hydrido, a phosphido, and a carbene ligand, is produced by multiple fragmentation of the diphosphine. This fragmentation appears related to the presence of the selenido ligand on the cluster, as the reaction of [Ru3(CO)12] with dpmb (not selenized) produces only carbonyl substitution by the phosphine to give [Ru3(CO)10(μ-dpmb)] (9). All the clusters synthesized have been characterized by spectroscopic techniques, and in some cases fluxional behavior has been detected in solution by NMR analysis. The structures of 1, 2, and 7−9 have been determined by X-ray diffraction methods.
