Group 6 Metal Complexes of the η5-Pentamethyl[60]fullerene

A molybdenum pentamethyl[60]fullerene bromo tricarbonyl complex, Mo(η 5 -C 60 Me 5 )Br(CO) 3 ( 3 ), was successfully synthesized by the reaction of C 60 Me 5 Br ( 2 ) with Mo(CO) 3 (EtCN) 3 . Treatment of 3 with I 2 afforded an iodo complex, Mo(η 5 -C 60 Me 5 )I(CO) 3 ( 4 ). The reaction employing C 60 Me 5 K ( 5 ) prepared from C 60 Me 5 H ( 1 ) and KH, followed by treatment with Mo(CO) 3 (EtCN) 3 and then Diazald, gave a nitrosyl complex, Mo(η 5 -C 60 Me 5 )(NO)(CO) 2 ( 6 ). Complex 6 was converted to a molybdenum(IV) complex, Mo(η 5 -C 60 Me 5 )Cl 2 (NO)(CO) ( 7 ), by the reaction with PCl 5 . A molybdenum(VI) complex, Mo(η 5 -C 60 Me 5 )O 2 Br ( 8 ), was obtained by exposure of 3 in air. Tungsten- and chromium-nitrosyl complexes, W(η 5 -C 60 Me 5 )(NO)(CO) 2 ( 9 ) and Cr(η 5 -C 60 Me 5 )(NO)(CO) 2 ( 10 ), were synthesized similarly to 6 . Complex 10 gave a dithiocarbonate complex, Cr(η 5 -C 60 Me 5 )(η 5 -S 2 COEt)(NO) ( 11 ) through the reaction among 10, ethanol, and carbon disulfide. Compounds 1, 3, 4, 6, 8, and 11 were characterized by X-ray crystallography.