10.1021/jacs.7b10325.s001
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
Journal contribution
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 CH 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.