Synthesis of the Hydrosilicon Species Via Oxidative Addition of Silylene Toward the Proton-Containing Molecules

The oxidative addition reaction of silylenes with proton-containing molecules is an effective method for synthesis of hydrosilicon species. Herein, amidinatoborylaminosilylenes (L)[(1,5-C8H14)B(R)N]Si [L=PhC(NtBu)(2); R=2,4,6-Me3C6H2 (1), 2,6-iPr(2)C(6)H(3) (2), 1-C10H15 (3)] were employed, each of which reacted with 1-(diphenylmethyl)-3-hydroxyazetidine to produce the derived alkoxyl hydrosilicon compounds (L)[(1,5-C8H14)B(R)N]Si(H)[O-cyclo-CH(CH2)(2)N(CHPh2)] (4 similar to 6), and with mercaptans as 2-naphthalenethiol, 4-fluorothiophenol, 2-chlorobenzenethiol to yield thiol hydrosilicon compounds (L)[(1,5-C8H14)B(R)N]Si(H)(SR') (7 similar to 14). Silylene 1 reacted with diphenylamine to give (L)[(1,5-C8H14)B(2,4,6-Me3C6H2)N]Si(H)(NPh2) (15). Compounds 4 similar to 15 have been characterized by NMR spectra and elemental analysis, of which 5, 7 and 11 were further confirmed by X-ray crystallography. Compounds 4 similar to 15 are the hydrosilicon species with novel structures and compositions, all of which are bonded by four different groups, being generated by the oxidative addition reaction via the silylene Si: center toward the respective O-H, S-H, and N-H bonds of the proton-containing molecules, where a mode of a charge reversal of the proton into the hydride group at the Si center is realized.