Photochemical Addition of C60 with Siliranes: Synthesis and Characterization of Carbosilylated and Hydrosilylated C60 Derivatives

摘要

Photochemical reactions of C₆₀ with siliranes (1a−d) afford adducts of four types (2a−5b) as carbosilylated and hydrosilylated C₆₀ derivatives. Characterization of these adducts was conducted using MS, UV, NMR spectroscopy, and single-crystal X-ray analyses. In particular, the first example of the crystal structure of a closed 1,2-adduct at the 5,6-ring junction of the C₆₀ cage is provided by single-crystal X-ray analysis of 3b. Electrochemical analyses also revealed unique redox properties of the products 2b−5b, which depend on the regiochemistry of the functionality, in addition to the substituents on the C₆₀ cage. Theoretical calculations offer bases for the experimentally observed redox properties and relative stabilities of the silylated products.