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 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.
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