Decarbonylation of Os 5 (CO) 14 (PPh 3 ) by 2 equiv of Me 3 NO/CH 3 CN at room temperature followed by reaction with C 60 in refluxing chlorobenzene produces Os 5 C(CO) 11 (PPh 3 )(µ 3 ,η 2 : η 2 :η 2 -C 60 ) (1) in 44% yield. Thermal treatment of 1 at 80 °C under 1 atm of carbon monoxide affords Os 5 C(CO) 12 (PPh 3 )(µ,η 2 :η 2 -C 60 ) (2) in good yield (72%). Upon thermolysis of 2 at 132 °C, 2 is cleanly reconverted to 1 (73%) by loss of a carbonyl ligand. Reaction of 1 with benzyl isocyanide at room temperature gives the addition product Os 5 C(CO) 11 (CNCH 2 C 6 H 5 )(PPh 3 )-(µ 3 ,η 2 :η 2 :η 2 -C 60 ) (3) in 85% yield. Thermolysis of 3 at 100 °C forms the isomeric Os 5 C(CO) 11 -(CNCH 2 C 6 H 5 )(PPh 3 )(µ,η 2 :η 2 -C 60 ) (4) in 64% yield. Treatment of 4 with 1 equiv of Me 3 NO/ CH 3 CN at room temperature followed by heating at 132 °C in chlorobenzene gives Os 5 C(CO) 10 (CNCH 2 C 6 H 5 )(PPh 3 )(µ 3 ,η 2 :η 2 :η 2 -C 60 ) (5) in 71% yield. Compound 5 can be alternatively prepared from the reaction of 1 with excess Ph 3 PdNCH 2 Ph at room temperature in 59% yield. Heating a chlorobenzene solution of 5 at 55 °C under 3 atm of carbon monoxide produces 4 as the only major product (16%). Treatment of Ru 5 C(CO) 11 (PPh 3 )(µ 3 ,η 2 :η 2 :η 2 -C 60 ) (1′) with benzyl isocyanide at room temperature forms Ru 5 C(CO) 11 (CNCH 2 C 6 H 5 )(PPh 3 )(µ 3 ,η 2 : η 2 :η 2 -C 60 ) (3′) in 90% yield. Reaction of 1′ with benzyl isocyanide at a slightly elevated temperature of 40 °C affords Ru 5 C(CO) 10 (CNCH 2 C 6 H 5 )(PPh 3 )(µ 3 ,η 2 :η 2 :η 2 -C 60 ) (5′) in an almost quantitative yield of 96%. Compounds 1-5, 3′, and 5′, isolated as crystalline solids, have been characterized by microanalytical and spectroscopic methods. Molecular structures of 1-4 and 5′ have been elucidated by X-ray crystallographic studies.
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