[(methylcyclopentadienyl)cobalt(III)(1,2-dicarba-closo-dodecaborane-1,2-dithiolate)] | 1400655-93-7

• 英文名称: [(methylcyclopentadienyl)cobalt(III)(1,2-dicarba-closo-dodecaborane-1,2-dithiolate)]
• 英文别名: [(methylcyclopentadienyl)cobalt(1,2-dicarba-closo-dodecaborane-1,2-dithiolato)]；[MeCpCo(S₂C₂B₁₀H₁₀)]；MeCpCoS2C2B10H10
• CAS: 1400655-93-7
• 化学式: C₈H₁₇B₁₀CoS₂
• 分子量: 344.458
• InChiKey: UPQCDYVYXARMOV-UHFFFAOYSA-N

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

• 作为反应物：
  描述：

  [(methylcyclopentadienyl)cobalt(III)(1,2-dicarba-closo-dodecaborane-1,2-dithiolate)] 、 丁炔二酸二甲酯 以 二氯甲烷 为溶剂， 反应 10.0h， 以92%的产率得到(MeCpCoS2C2B10H10)(MeO2C-C=C-CO2Me)
  参考文献：
  名称：

  Reactivity of two MeCp-cobalt complexes containing 1,2-dicarba-closo-dodecaborane-1,2-dichalcogenolate (S2C2B10H10)2– units toward alkynes

  摘要：

  Treatment of o-carborane, n-butyllithium, sulfur, and MeCpCo(CO)I-2 under argon leads to twoMeCp-cobalt complexes MeCpCoS2C2B10H10 (I) and (MeCp)(2)Co2S2C2B10H10 (II). Complex I reacts with phenylacetylene or dimethyl acetylene dicarboxylate to afford B-H activitied complex (MeCpCoS2C2B10H9)(Ph-C-CH2) (III) and addition complex (MeCpCoS2C2B10H10)(MeO2C-C=C-CO2Me) (IV), respectively. Complex II reacts neither with phenylacetylene nor with dimethyl acetylene dicarboxylate. Complexes II-IV have been characterized by elemental analysis, mass, NMR spectroscopy, IR, and X-ray structural analyses (CIF files CCDC nos. 1045892 (II), 1045893 (III) and 1045894 (IV)).

  DOI：

  10.1134/s1070328415090092
• 作为产物：
  描述：

  1,2-dicarba-closo-dodecaborane(12) 、 MeCpCo(CO)I2 、 sulfur 在 正丁基锂 作用下， 以 乙醚 、 四氢呋喃 为溶剂， 反应 1.0h， 以87%的产率得到[(methylcyclopentadienyl)cobalt(III)(1,2-dicarba-closo-dodecaborane-1,2-dithiolate)]
  参考文献：
  名称：

  Reactivity of two MeCp-cobalt complexes containing 1,2-dicarba-closo-dodecaborane-1,2-dichalcogenolate (S2C2B10H10)2– units toward alkynes

  摘要：

  Treatment of o-carborane, n-butyllithium, sulfur, and MeCpCo(CO)I-2 under argon leads to twoMeCp-cobalt complexes MeCpCoS2C2B10H10 (I) and (MeCp)(2)Co2S2C2B10H10 (II). Complex I reacts with phenylacetylene or dimethyl acetylene dicarboxylate to afford B-H activitied complex (MeCpCoS2C2B10H9)(Ph-C-CH2) (III) and addition complex (MeCpCoS2C2B10H10)(MeO2C-C=C-CO2Me) (IV), respectively. Complex II reacts neither with phenylacetylene nor with dimethyl acetylene dicarboxylate. Complexes II-IV have been characterized by elemental analysis, mass, NMR spectroscopy, IR, and X-ray structural analyses (CIF files CCDC nos. 1045892 (II), 1045893 (III) and 1045894 (IV)).

  DOI：

  10.1134/s1070328415090092

文献信息

• Cobalt-promoted B–H and C–H activation in the three-component reactions of 16-electron cobalt carboranedithiolate, alkyne and bronsted acids
  作者：Rui Zhang、Lin Zhu、Zhenzhong Lu、Hong Yan

  DOI：10.1016/j.jorganchem.2015.06.013

  日期：2015.12

  isolated where L1–L3 loses one proton to provide 3 electrons to metal and alkyne is reduced to olefin. If L4 and L5 are used, products 4a or 4b are generated where the Bronsted acid is not observed but the alkyne is reduced to sp3 and forms a five-membered ring with Co center. Allenes (L6 and L7) lead to 5a(L6) and 5a(L7) where an allyl unit is coordinated to metal. In case of CpH (L8), compounds 6a and 6b

  Cp ＃ Co（S 2 C 2 B 10 H 10）（Cp ＃ = Cp，1a ; MeCp，1b ; Me 4 Cp，1c ; Me 5 Cp，1d），丙酸甲酯（2）和报道了布朗斯台德酸有机配体（L1-L8）。1a和1b只能导致在碳硼烷上以环戊二烯基或甲基-环戊二烯基作为官能团在环境温度下进行选择性B-官能化，收率很高。根据所使用的布朗斯台德酸（L1-L8）的类型，可以获得四种包含B-C键的产品。如果选择了较强的配位体L1-L3，则可以分离化合物3a（L1-L3）和3b（L1-L3），其中L1-L3失去一个质子，从而为金属提供3个电子，炔烃被还原为烯烃。如果使用L4和L5，则生成产物4a或4b，其中未观察到布朗斯台德酸，但炔烃还原为sp 3并与Co中心形成一个五元环。烯丙基（L6和L7）导致5a（L6）和5a（L7），其中烯丙基单元与金属配位。在CpH（L8）的情况下，会生成含有原位的化
• Reactivity of 16-electron half-sandwich cobalt compounds containing a chelating 1,2-dicarba-closo-dodecaborane-1,2-dithiolate ligand towards methyl propiolate and dithio ligands
  作者：Rui Zhang、Lin Zhu、Zhenzhong Lu、Hong Yan、Vladimir I. Bregadze

  DOI：10.1039/c2dt31425h

  日期：——

  The reaction of the 16-electron half-sandwich complex MeCpCo(S2C2B10H10) (1b; MeCp = methylcyclopentadienyl) and methyl propiolate (HCCCO2Me) at ambient temperature leads to MeCpCo(S2C2B10H9)(CHCHCO2Me) (2), MeCpCo(S2C2B10H8)(CHCHCO2Me)2 (3), MeCpCo(S2C2B10H9)[MeO2CCCH(MeO2C)CCH)](CHCHCO2Me) (4) and MeCpCo(S2C2B10H9)(CH2CCO2Me) (5). The reaction of Me4CpCo(S2C2B10H10) (1c; Me4Cp = tetramethylcyclopentadienyl) and the alkyne gives rise to Me4CpCo(S2C2B10H10)[MeO2CCCH(MeO2C)CCH] (6) and Me4CpCo (S2C2B10H9)(CH2CCO2Me) (7). Both 2 and 3 are 16-electron complexes but containing a B(3)-substituted o-carborane-1,2-dithiolate ligand in 2 and a B(3,6)-disubstituted o-carborane-1,2-dithiolate ligand in 3, respectively. In 4 and 6, two alkynes are inserted into one Co–S bond to meet an 18 electron configuration at metal, however, 4 has one B-substitution at carborane. Both 5 and 7 have the same structural type bearing a B–CH2 unit. The reactions of Cp#Co(E2C2B10H10) [Cp# = Cp (1a), MeCp (1b), Me4Cp (1c) and Me5Cp (1d); E = S, Se] with 2-methylpropanedithioic acid (L1) or pyrrolidine-1-carbodithioic acid (L2) lead to Co[S2CCH(CH3)2]3 (8) or Co[S2CN(CH2)4]3 (9), respectively, in an octahedral geometry. The three-component reactions of 1a–1d, methyl propiolate and L1 or L2 afford seven new compounds Cp#Co[S2C2B10H10(CHCHCO2Me)][S2CCH(CH3)2] [Cp# = Cp (10a), MeCp (10b) and Me4Cp (10c)], [S2CCH(CH3)2]2Co(S2C2B10H10)(CHCCO2Me)CpCo[S2CCH(CH3)2]} (11a), Cp#Co[S2C2B10H10(CHCHCO2Me)][S2CN(CH2)4] [Cp# = Cp (12a), MeCp (12b) and Me4Cp (12c)]. All 10a–10c and 12a–12c contain one deprotonated L1 or L2 ligand and one reduced alkyne. 11a has two 18-electron Co centers linked by one reduced alkyne. One metal is coordinated by an o-carborane-1,2-dithiolate and two L1 ligands, and the other is coordinated by one L1 ligand and one η5-Cp unit. In both two- and three-component reactions the reactivity of the 16-electron half-sandwich complexes Cp#Co(S2C2B10H10) is dependent on the size of the Cp# unit. All compounds were fully characterized by spectroscopic techniques and elemental analysis. The solid-state structures of 4, 5, 7, 10a and 11a were further determined by X-ray crystallographic analysis.

  16电子半三明治配合物MeCpCo(S2C2B10H10) (1b; MeCp = 甲基环戊二烯基)与甲基丙炔酸酯(HCCCO2Me)在室温下反应，生成MeCpCo(S2C2B10H9)(CHCHCO2Me) (2)、MeCpCo(S2C2B10H8)(CHCHCO2Me)2 (3)、MeCpCo(S2C2B10H9)[MeO2CCCH(MeO2C)CCH](CHCHCO2Me) (4)和MeCpCo(S2C2B10H9)( CCO2Me) (5)。Me4CpCo(S2C2B10H10) (1c; Me4Cp = 四甲基环戊二烯基)与炔烃的反应生成Me4CpCo(S2C2B10H10)[MeO2CCCH(MeO2C)CCH] (6)和Me4CpCo(S2C2B10H9)( CCO2Me) (7)。2和3均为16电子配合物，但2中含有B(3)-取代的o-硼烷-1,2-二硫配体，而3中含有B(3,6)-二取代的o-硼烷-1,2-二硫配体。在4和6中，两种炔烃插入一个Co–S键，以达到金属的18电子构型，但4在车伯烷上有一个B取代。5和7具有相同的结构类型，含有B–CH2单元。Cp#Co(E2C2B10H10) [Cp# = Cp (1a)、MeCp (1b)、Me4Cp (1c)和Me5Cp (1d); E = S, Se]与2-甲基丙烯二硫酸(L1)或呋喃-1-羧基二硫酸(L2)的反应分别生成Co[S2CCH(CH3)2]3 (8)或Co[S2CN( )4]3 (9)，呈八面体几何结构。1a–1d、甲基丙炔酸酯及L1或L2的三组分反应生成七个新化合物Cp#Co[S2C2B10H10(CHCHCO2Me)][S2CCH( )2] [Cp# = Cp (10a)、MeCp (10b)和Me4Cp (10c)]、[S2CCH( )2]2Co(S2C2B10H10)(CHCCO2Me)CpCo[S2CCH( )2]} (11a)以及Cp#Co[S2C2B10H10(CHCHCO2Me)][S2CN( )4] [Cp# = Cp (12a)、MeCp (12b)和Me4Cp (12c)]。所有10a–10c和12a–12c均包含一个去质子化的L1或L2配体和一个还原的炔烃。11a具有两个18电子的Co中心，通过一个还原的炔烃连接。一个金属由一个o-硼烷-1,2-二硫配体和两个L1配体配位，另一个由一个L1配体和一个η5-Cp单元配位。在两组分和三组分反应中，16电子半三明治配合物Cp#Co(S2C2B10H10)的反应性取决于Cp#单元的大小。所有化合物均通过光谱技术和元素分析进行了充分表征。4、5、7、10a和11a的固态结构进一步通过X射线晶体学分析确定。
• Reactivity of Two 16e Half-Sandwich Cobalt Complexes Containing 1,2-Dicarba-closo-Dodecaborane-1,2-Dichalcogenolate (E2C2B10H10)2– (E = S, Se) Units toward Triphenylphosphine
  作者：H. D. Ye、Y. L. Zhan、J. Liang、T. Y. Ye、D. Zhang、H. N. Peng、J. R. Hu

  DOI：10.1134/s1070328418070047

  日期：2018.7

  Cp*Co(CO)I2) (Cp* = pentamethylcyclopentadienyl) under argon leads to half-sandwich carborane complex MeCpCo(S2C2B10H10) (I) (or Cp*Co(Se2C2B10H10) (II)). Complex I reacts with triphenylphosphine to afford addition product MeCpCo(S2C2B10H10)(PPh3) (III). However, II does not react with triphenylphosphine. Complexes II and III have been characterized by elemental analysis, mass, NMR spectroscopy, IR and

  在氩气下处理邻碳硼烷，正丁基锂，硫（或硒）和MeCpCo（CO）I 2（或Cp * Co（CO）I 2）（Cp * =五甲基环戊二烯基）会导致半夹心碳硼烷络合物MeCpCo（ S 2 C 2 B 10 H 10）（I）（或Cp * Co（Se 2 C 2 B 10 H 10）（II））。配合物I与三苯膦反应生成加成产物MeCpCo（S 2 C 2 B 10 H 10）（PPh 3）（III）。但是，II不与三苯膦反应。配合物II和III已通过元素分析，质谱，NMR光谱，IR和X射线结构分析（CIF文件CCDC No. 1571705（II）和1571706（III））进行了表征。