Facile Conversion of Bis-Silylene to Cyclic Silylene Isomers: Unexpected C–N and C–H Bond Cleavage Yuzhong Wang Hunter P. Hickox Yaoming Xie Pingrong Wei Henry F. Schaefer Gregory H. Robinson 10.1021/jacs.7b10325.s001 https://acs.figshare.com/articles/journal_contribution/Facile_Conversion_of_Bis-Silylene_to_Cyclic_Silylene_Isomers_Unexpected_C_N_and_C_H_Bond_Cleavage/5573215 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. 2017-11-01 00:00:00 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