Zhong, Wei Yang, Qiwu Shang, Yi Liu, Guifeng Zhao, Haitao Li, Yizhi Yan, Hong 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) 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>CCR<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>CCR<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 PhCCCO<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>CCNSO<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>. 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
    https://acs.figshare.com/articles/journal_contribution/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_/2484226
10.1021/om300735d.s003