10.1021/jacs.7b10325.s002 Yuzhong Wang Yuzhong Wang Hunter P. Hickox Hunter P. Hickox Yaoming Xie Yaoming Xie Pingrong Wei Pingrong Wei Henry F. Schaefer Henry F. Schaefer Gregory H. Robinson Gregory H. Robinson Facile Conversion of Bis-Silylene to Cyclic Silylene Isomers: Unexpected C–N and C–H Bond Cleavage American Chemical Society 2017 isomeric 3 Cyclic Silylene Isomers carbene ligand five-membered Facile Conversion four-membered cyclic silylene insertion THF carbene-stabilized diiodo-bis-silylene ratio phenyl method Bis-Silylene imidazole ring toluene olefinic sulfur-containing Unexpected Cleavage Bond zwitterionic silylene ring silicon bond nature thiolate 1 2017-11-01 00:00:00 Dataset https://acs.figshare.com/articles/dataset/Facile_Conversion_of_Bis-Silylene_to_Cyclic_Silylene_Isomers_Unexpected_C_N_and_C_H_Bond_Cleavage/5573212 Reaction of thiolate <b>1</b> with carbene-stabilized diiodo-bis-silylene (<b>2</b>) (in a 2:1 ratio) in THF unexpectedly gives both the first five-membered, sulfur-containing, zwitterionic silylene ring (<b>3</b>) via insertion of the “Si<sup>I</sup><sub>2</sub>” unit of <b>2</b> into the olefinic CH bond of the imidazole ring of <b>1</b> and four-membered cyclic silylene (<b>4</b>) via insertion of a silicon­(I) atom of <b>2</b> into the C<sub>phenyl</sub>N bond of the carbene ligand. The parallel reaction in toluene only gives <b>3</b> as the major product. The nature of the bonding in isomeric <b>3</b> and <b>4</b> was probed by experimental and theoretical methods.