Abstract
Reactions of the triosmium clusters Os3(CO)10(μ-dppm) [dppm = bis(diphenylphosphino)methane] and Os3(CO)8(μ3-Ph2PCH2P(Ph)C6H4)(μ-H) with Ph3GeH are described. With Os3(CO)10(μ-dppm) at 110 °C the oxidative-addition product Os3(CO)9(GePh3)(μ-dppm)(μ-H) (1) initially results, but further decarbonylates upon prolonged heating to give 46-electron Os3(CO)7(GePh3)(μ3-Ph2PCH2P(Ph)C6H4)(μ-H)2 (2) resulting from C–H bond activation of the diphosphine. The pre-activated Os3(CO)8(μ3-Ph2PCH2P(Ph)C6H4)(μ-H) reacts with Ph3GeH under milder conditions (40 °C) to afford Os3(CO)8(GePh3)2(μ-dppm)(μ-H)2 (3) together with 1. Cluster 3 converts into 2 upon heating and the direct reaction between Os3(CO)8(μ3-Ph2PCH2P(Ph)C6H4)(μ-H) and Ph3GeH at 110 °C also produces 2. All these clusters have been structurally characterized by single crystal X-ray diffraction analysis.
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