10.1021/acs.organomet.6b00208.s003
Chenting Yan
Chenting
Yan
Zheng Xu
Zheng
Xu
Xu-Qiong Xiao
Xu-Qiong
Xiao
Zhifang Li
Zhifang
Li
Qiong Lu
Qiong
Lu
Guoqiao Lai
Guoqiao
Lai
Mitsuo Kira
Mitsuo
Kira
Reactions of an Isolable Dialkylstannylene with Carbon
Disulfide and Related Heterocumulenes
American Chemical Society
2016
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
2016-04-21 13:06:22
Dataset
https://acs.figshare.com/articles/dataset/Reactions_of_an_Isolable_Dialkylstannylene_with_Carbon_Disulfide_and_Related_Heterocumulenes/3188008
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>.