Complexation and C−H/C−P Bond Activation of the (PPh₂)C₆₀H Molecule on Triosmium Carbonyl Clusters

Reaction of (PPh2)C60H (1) and Os3(CO)10(NCMe)2 produces Os3(CO)10(μ,η3-(PPh2)C60H) (2), with one edge of the triosmium cluster bridged by the phosphine group and one CC double bond of 1. Treating compound 1 with Os3(CO)11(NCMe) affords Os3(CO)11((PPh2)C60H) (3), with the phosphine ligand coordinated to one osmium atom. Thermolysis of 2 in refluxing chlorobenzene leads to orthometalation of one phenyl group and C−H/C−P bond activation of the (PPh2)C60H ligand to afford the phosphido cluster (μ-H)2Os3(CO)9(μ3,η2-PPh(C6H4)) (4) and C60 molecule. Compound 3 undergoes thermal decarbonylation in refluxing toluene to produce 2. The molecular structures of compounds 1-BH3, 2, and 3 were determined by an X-ray diffraction study.