Seok-Bong Choi, P. Boudjouk, Youlin Pan
Sep 13, 1999
Citations
0
Influential Citations
5
Citations
Journal
Organometallics
Abstract
The X-ray crystal structure determination of the trapping products of 1-methyl-1,1-dihydrido-5-potassio-2,3,4,5-tetraphenyl-1-silacyclopentadiene silicate, [Ph4C4SiMeH2-]·[K+] (2), with excess dimethylchlorosilane shows enantiomers of 1-methyl-2-(dimethylsilyl)-2,3,4,5-tetraphenyl-1-silacyclo-3-pentene (5a1, 5a2) in a ratio of 1:1. The trans orientation of the H−Si−C−H linkage is confirmed by torsional angles of two hydrogens (∠HSiCH = 140.7°). Structural characterization of the enantiomers of 1-(bis(trimethylsilyl)amino)-5-methyl-2,3,4,5-tetraphenyl-1-silacyclo-3-pentene (10a, 10b), obtained as major products from the reaction of 1-(bis(trimethylsilyl)amino)-5-sodio-2,3,4,5-tetraphenyl-1-silacyclo-3-pentene (9) with excess MeI indicate the cis arrangement of the H−Si−C−H linkage (∠HSiCH = 29.8°). All of the reaction products can be envisioned as resulting from a pathway involving pentacoordinate anionic intermediates that undergo pseudorotation, 1,2-hydride migration from silicon to carbon, and quenching...