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Facile Conversion of Bis-Silylene to Cyclic Silylene Isomers: Unexpected C–N and C–H Bond Cleavage

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posted on 2017-11-01, 00:00 authored by Yuzhong Wang, Hunter P. Hickox, Yaoming Xie, Pingrong Wei, Henry F. Schaefer, Gregory H. Robinson
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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