The chemistry of the selenium-containing cluster [Ru4(µ4-Se)2(CO)8(µ-CO)3]: crystal structures of [Ru3(µ3-Se)2(CO)7(Ph2PC2PPh2)], [Ru4(µ4-Se)2(CO)10(SbPh3)] and [Ru3(µ3-Se)2(CO)9]

Abstract

The selenium-containing cluster [Ru₄(µ₄-Se)₂(CO)₈(µ-CO)₃]1 may be readily prepared by vacuum pyrolysis of [Ru₃(CO)₁₂] with PhSeSePh at 185 °C. The subsequent reaction of 1 with the bidentate phosphine ligand bis(diphenylphosphino)acetylene (dppa) affords the orange triruthenium cluster [Ru₃(µ₃-Se)₂(CO)₇(dppa)]2, in 80% yield. Complex 2 crystallises in the space group P with a= 12.059(3), b= 12.274(3), c= 13.172(5)Å, α= 66.78(2), β= 83.21(3), γ= 89.30(2)° and Z= 2. Treatment of complex 1 with triphenylantimony, SbPh₃, yields the antimony-substituted cluster [Ru₄(µ₄-Se)₂(CO)₁₀(SbPh₃)]3, in quantitative yield. Complex 3 crystallises in the space group P with a= 9.474(4), b= 12.456(3), c= 14.913(5)Å, α= 91.89(2), β= 93.88(3), γ= 109.99(3)° and Z= 2. Reaction of cluster 1 with carbon monoxide at room temperature and 70 atm affords the triruthenium selenido-bridged cluster [Ru₃(µ₃-Se)₂(CO)₉]4. Complex 4 crystallises in the space group P with a= 6.887(3), b= 9.606(7), c= 13.567(9)Å, α= 82.48(6), β= 84.91(4), γ= 68.85(5)° and Z= 2.