Abstract
Addition of 2,2'-bis(diphenylphosphino)propane, Ph2PC(Me)2PPh2 (dppmMe2), to Os3(CO)10(MeCN)2 at room temperature affords Os3(CO)10{μ-Ph2PC(Me)2PPh2} (1-Me2), whose X-ray diffraction has been established and found to contain a bridging diphosphine ligand. Heating 1-Me2 in toluene results in the formation of the expected orthometalated addition product Os3(CO)8{μ3-Ph2PC(Me)2P(Ph)C6H4}(μ-H) (2-Me2) in only trace amounts, with the face-capped cluster Os3(CO)9{μ3-PhPC(Me)2P(Ph)C6H4} (3-Me2) formed as the major product as a result of elimination of benzene. The conversion of 1-Me2 to 2-Me2 has been investigated by density functional theory (DFT) calculations and the potential energy surface has been mapped out. The observed reactivity in the dppmMe2-substituted cluster 1-Me2 is compared with the related dppmH2- and dppmHMe-substituted triosmium complexes.
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