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

Reaction of (PPh 2 )C 60 H ( 1 ) and Os 3 (CO) 10 (NCMe) 2 produces Os 3 (CO) 10 (μ,η 3 -(PPh 2 )C 60 H) ( 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 Os 3 (CO) 11 (NCMe) affords Os 3 (CO) 11 ((PPh 2 )C 60 H) ( 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 (PPh 2 )C 60 H ligand to afford the phosphido cluster (μ-H) 2 Os 3 (CO) 9 (μ 3,η 2 -PPh(C 6 H 4 )) ( 4 ) and C 60 molecule. Compound 3 undergoes thermal decarbonylation in refluxing toluene to produce 2 . The molecular structures of compounds 1-BH 3, 2, and 3 were determined by an X-ray diffraction study.