Decarbonylation of Os5(CO)14(PPh3) by 2 equiv of Me3NO/CH3CN at room temperature followed by reaction with C60 in refluxing chlorobenzene produces Os5C(CO)11(PPh3)(μ3, η2:η2:η2-C60) (1) in 44% yield. Thermal treatment of 1 at 80°C under 1 atm of carbon monoxide affords Os5C(CO)12(PPh3)(μ,η2: η2-C60) (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 Os5C(CO)11(CNCH2C6H5) (PPh3)- (μ3,η2:η2:η2- C60) (3) in 85% yield. Thermolysis of 3 at 100°C forms the isomeric Os5C(CO)11(CNCH2C6H5) (PPh3) (μ,η2:η2-C60) (4) in 64% yield. Treatment of 4 with 1 equiv of Me3NO/CH3CN at room temperature followed by heating at 132°C in chlorobenzene gives Os5C(CO)10(CNCH2C6H5) (PPh3) (μ3,η2:η2:η2- C60) (5) in 71% yield. Compound 5 can be alternatively prepared from the reaction of 1 with excess Ph3P=NCH2Ph at room temperature in 59% yield. Heating a chlorobenzene solution of 5 at 55°C under 3 atm carbon monoxide produces 4 as the only major product (16%). Treatment of Ru5C(CO)11(PPh3)(μ3, η2:η2:η2-C60) (1′) with benzyl isocyanide at room temperature forms Ru5C(CO)11(CNCH2C6H5) (PPh3) (μ3,η2:η2:η2- C60) (3′) in 90% yield. Reaction of 1′ with benzyl isocyanide at a slightly elevated temperature of 40°C affords Ru5C(CO)10(CNCH2C6H5) (PPh3) (μ3,η2:η2:η2- C60) (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.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry