(η⁵-cyclopentadienyl)Co(1,2-dicarba-closo-dodecaborane-1-thiolate-2-(SNCOOMe)) | 1398553-71-3

• 英文名称: (η⁵-cyclopentadienyl)Co(1,2-dicarba-closo-dodecaborane-1-thiolate-2-(SNCOOMe))
• 英文别名: CpCo(S₂C₂B₁₀H₁₀)(CONOMe)
• CAS: 1398553-71-3
• 化学式: C₉H₁₈B₁₀CoNO₂S₂
• 分子量: 403.483
• InChiKey: KITRSYYKEVSIIJ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  (η5-cyclopentadienyl)Co(1,2-dicarba-closo-dodecaborane-1,2-dithiolate) 、 叠氮基甲酸甲酯 以 甲苯 为溶剂， 反应 24.0h， 以60.7%的产率得到(η⁵-cyclopentadienyl)Co(1,2-dicarba-closo-dodecaborane-1-thiolate-2-(SNCOOMe))
  参考文献：
  名称：

  Synthesis and Reactivity of the Imido-Bridged Metallothiocarboranes CpCo(S₂C₂B₁₀H₁₀)(NSO₂R)

  摘要：

  The reactions of the 16-electron half-sandwich complex CpCo(S2C2B10H10) (1) (Cp: cyclopentadienyl) with sulfonyl azides (p-toluenesulfonyl azide, TsN3; methanesulfonyl azide, MsN3) in refluxing dichloromethane or at ambient temperature lead to imido-bridged adducts CpCo(S2C2B10H10) (NSO2R) (2a, R = 4-MePh; 2h, R = Me) which can convert to the tetraazadiene cobalt complexes CpCoN4(SO2R)(2) (3a, R = 4-MePh; 3b, R = Me) in the presence of excess azide if heated. The reactions of 1 with acyl azides (methyl azidoformate and benzoyl azide) lead to CpCo(S2C2B10H10)(CONR) (4a, R = OMe; 4b, R = Ph) with a newly-generated five-membered metallacyclic ring Co-S-N-C-O. Complexes 2a and 2b show further reactivity toward alkynes to give rise to the insertion products CpCo(S2C2B10H10)(R1C=CR2) (NSO2R) (R-1 = COOMe, R-2 = H, R = 4-MePh, 5a, R = Me, 5b; R-1 = R-2 = COOMe, R = 4-MePh, 6a, R = Me, 6h; R-1 = COOMe, R-2 = Ph, R = 4-MePh, 8a, R = Me, 8b) formed by alkyne addition to a Co-S bond to generate a Co-C-C-S four-membered ring and CpCo(S2C2B10H10) (R1C=CR2NSO2R) (R-1 = H, R-2 = Ph, R = 4-MePh, 7a, R = Me, 7b; R-1 = COOMe, R-2 = Ph, R = 4-MePh, 9a, R = Me, 9b) 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 CCO2Me, the products with insertion into both Co-S and Co-N bonds are isolated. Interestingly, if tert-butylacetylene is used, CpCo(S2C2B10H10)(R1R2C=CNSO2R) (R-1 = tBu, R-2 = H, R = 4-MePh, 10a, R = Me, 10b) 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 2a, 3a, 313, 4a, 4b, 5a, 6a, 7a, 7b, 8a, 9a, 9b, and 10b.

  DOI：

  10.1021/om300735d