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

Author:
Wang, Yuzhong, Hickox, Hunter P., Xie, Yaoming, Wei, Pingrong, Schaefer, Henry F., Robinson, Gregory H.
Source:
Journal of the American Chemical Society 2017 v.139 no.45 pp. 16109-16112
ISSN:
1520-5126
Subject:
carbenes, chemical bonding, cleavage (chemistry), isomers, ligands, silicon, toluene, zwitterions
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.
Agid:
5860396