10.1021/om300735d.s004
Wei Zhong
Wei
Zhong
Qiwu Yang
Qiwu
Yang
Yi Shang
Yi
Shang
Guifeng Liu
Guifeng
Liu
Haitao Zhao
Haitao
Zhao
Yizhi Li
Yizhi
Li
Hong Yan
Hong
Yan
Synthesis and Reactivity
of the Imido-Bridged Metallothiocarboranes
CpCo(S<sub>2</sub>C<sub>2</sub>B<sub>10</sub>H<sub>10</sub>)(NSO<sub>2</sub>R)
American Chemical Society
2012
2R
4 b
2 b show
bond
insertion
Ph
azide
R 1
9 b
CpCo
10 b
MePh
DFT
3 b
Co
R 2
COOMe
7 b
NSO
2012-09-24 00:00:00
Dataset
https://acs.figshare.com/articles/dataset/Synthesis_and_Reactivity_of_the_Imido_Bridged_Metallothiocarboranes_CpCo_S_sub_2_sub_C_sub_2_sub_B_sub_10_sub_H_sub_10_sub_NSO_sub_2_sub_R_/2484229
The reactions of the 16-electron half-sandwich complex
CpCo(S<sub>2</sub>C<sub>2</sub>B<sub>10</sub>H<sub>10</sub>) (<b>1</b>) (Cp: cyclopentadienyl) with sulfonyl azides (<i>p</i>-toluenesulfonyl azide, TsN<sub>3</sub>; methanesulfonyl azide, MsN<sub>3</sub>) in refluxing dichloromethane or at ambient temperature lead
to imido-bridged adducts CpCo(S<sub>2</sub>C<sub>2</sub>B<sub>10</sub>H<sub>10</sub>) (NSO<sub>2</sub>R) (<b>2a</b>, R = 4-MePh; <b>2b</b>, R = Me) which can convert to the tetraazadiene cobalt
complexes CpCoN<sub>4</sub>(SO<sub>2</sub>R)<sub>2</sub> (<b>3a</b>, R = 4-MePh; <b>3b</b>, R = Me) in the presence of excess
azide if heated. The reactions of <b>1</b> with acyl azides
(methyl azidoformate and benzoyl azide) lead to CpCo(S<sub>2</sub>C<sub>2</sub>B<sub>10</sub>H<sub>10</sub>)(CONR) (<b>4a</b>, R = OMe; <b>4b</b>, R = Ph) with a newly-generated five-membered
metallacyclic ring Co–S–N–C–O. Complexes <b>2a</b> and <b>2b</b> show further reactivity toward alkynes
to give rise to the insertion products CpCo(S<sub>2</sub>C<sub>2</sub>B<sub>10</sub>H<sub>10</sub>)(R<sub>1</sub>CCR<sub>2</sub>) (NSO<sub>2</sub>R) (R<sub>1</sub> = COOMe, R<sub>2</sub> = H, R
= 4-MePh, <b>5a</b>, R = Me, <b>5b</b>; R<sub>1</sub> =
R<sub>2</sub> = COOMe, R = 4-MePh, <b>6a</b>, R = Me, <b>6b</b>; R<sub>1</sub> = COOMe, R<sub>2</sub> = Ph, R = 4-MePh, <b>8a</b>, R = Me, <b>8b</b>) formed by alkyne addition to
a Co–S bond to generate a Co–C–C–S four-membered
ring and CpCo(S<sub>2</sub>C<sub>2</sub>B<sub>10</sub>H<sub>10</sub>)(R<sub>1</sub>CCR<sub>2</sub>NSO<sub>2</sub>R) (R<sub>1</sub> = H, R<sub>2</sub> = Ph, R = 4-MePh, <b>7a</b>, R = Me, <b>7b</b>; R<sub>1</sub> = COOMe, R<sub>2</sub> = Ph, R = 4-MePh, <b>9a</b>, R = Me, <b>9b</b>) formed by alkyne insertion into
a Co–N bond to generate a Co–C–C–N–S
five-membered ring. In the case of PhCCCO<sub>2</sub>Me, the
products with insertion into both Co–S and Co–N bonds
are isolated. Interestingly, if <i>tert</i>-butylacetylene
is used, CpCo(S<sub>2</sub>C<sub>2</sub>B<sub>10</sub>H<sub>10</sub>)(R<sub>1</sub>R<sub>2</sub>CCNSO<sub>2</sub>R) (R<sub>1</sub> = <i>t</i>Bu, R<sub>2</sub> = H, R = 4-MePh, <b>10a</b>, R = Me, <b>10b</b>) are generated by insertion of terminal
carbon into a Co–N bond to form four-membered ring Co–C–N–S.
The insertion pathways of these reactions have been discussed on the
basis of DFT calculations. All the new complexes were fully characterized,
and X-ray structural analyses were performed for <b>2a</b>, <b>3a</b>, <b>3b</b>, <b>4a</b>, <b>4b</b>, <b>5a</b>, <b>6a</b>, <b>7a</b>, <b>7b, 8a</b>, <b>9a</b>, <b>9b</b>, and <b>10b</b>.