Reactions of an Isolable Dialkylstannylene with Carbon
Disulfide and Related Heterocumulenes
Chenting Yan
Zheng Xu
Xu-Qiong Xiao
Zhifang Li
Qiong Lu
Guoqiao Lai
Mitsuo Kira
10.1021/acs.organomet.6b00208.s001
https://acs.figshare.com/articles/journal_contribution/Reactions_of_an_Isolable_Dialkylstannylene_with_Carbon_Disulfide_and_Related_Heterocumulenes/3187999
The reaction of isolable
dialkylstannylene <b>1</b> with
an excess amount of CS<sub>2</sub> produces an isomeric mixture of
3,3′-distanna-2,2′,4,4′-tetrathiabicyclobutylidene <b>8</b> and 3,7-distanna-2,4,6,8-tetrathiabicyclo[3.3.0]oct-1(5)-ene <b>9</b> with a ratio depending on the reaction conditions. Compounds <b>8</b> and <b>9</b> are separated by column chromatography
and characterized by NMR spectroscopy and X-ray crystallography. Detailed
investigation of the reaction has revealed that the initial product
is <b>8</b>, which isomerizes to <b>9</b> irreversibly
under the catalytic influence of <b>1</b> as a Lewis acid. The
above view is supported by the theoretical DFT calculations. Treatment
of <b>1</b> with ArNCO [Ar = 2,6-<i>i</i>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>] affords the corresponding
carbamoyl(hydroxyl)stannane <b>11</b> via the hydrolysis
of the corresponding silaaziridinone formed by the [1 + 2] cycloaddition
reaction of <b>1</b> with the NC double bond of the
isocyanate. Stannylene <b>1</b> reacts with ArNCS,
giving a mixture of complex products, while <b>1</b> does not
react with CO<sub>2</sub>.
2016-04-21 13:06:15
distanna
ArN
Carbon Disulfide
isomeric mixture
column chromatography
Compounds 8
Stannylene 1
isolable dialkylstannylene 1
Lewis acid
CO 2
reaction conditions
NMR spectroscopy
CS 2
DFT calculations
Isolable Dialkylstannylene
Related Heterocumulenes