Facile Conversion of Bis-Silylene to Cyclic Silylene Isomers: Unexpected C-N and C-H Bond Cleavage
Yuzhong Wang1, Hunter P Hickox1, Yaoming Xie1
1Department of Chemistry and the Center for Computational Chemistry, The University of Georgia , Athens, Georgia 30602-2556, United States.
Abstract:
Reaction of thiolate 1 with carbene-stabilized diiodo-bis-silylene (2) (in a 2:1 ratio) in THF unexpectedly gives both the first five-membered, sulfur-containing, zwitterionic silylene ring (3) via insertion of the "SiI2" unit of 2 into the olefinic C-H bond of the imidazole ring of 1 and four-membered cyclic silylene (4) via insertion of a silicon(I) atom of 2 into the Cphenyl-N bond of the carbene ligand. The parallel reaction in toluene only gives 3 as the major product. The nature of the bonding in isomeric 3 and 4 was probed by experimental and theoretical methods.
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