cobalt(III)(tetramethylene dithiocarbamate)3 | 24412-38-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: cobalt(III)(tetramethylene dithiocarbamate)3
• 英文别名: cobalt(3+);pyrrolidine-1-carbodithioate
• CAS: 24412-38-2
• 化学式: C₁₅H₂₄CoN₃S₆
• 分子量: 497.765
• InChiKey: WKOHUOCIZKJNLL-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  2.74
• 重原子数：
  25
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  109
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  cobalt(III)(tetramethylene dithiocarbamate)3 以 二氯甲烷 为溶剂， 生成 [Co(κ²-PyDT)₂]
  参考文献：
  名称：

  Bond; Hendrickson; Martin, Inorganic Chemistry, 1983, vol. 22, # 23, p. 3440 - 3446

  摘要：

  DOI：
• 作为产物：
  描述：

  1-吡咯烷二硫代氨基甲酸 、 (η5-cyclopentadienyl)Co(1,2-dicarba-closo-dodecaborane-1,2-dithiolate) 以 not given 为溶剂， 生成 cobalt(III)(tetramethylene dithiocarbamate)3
  参考文献：
  名称：

  Cobalt-Promoted B–H and C–H Activation: Facile B–C Coupling of Carboranedithiolate and Cyclopentadienyl

  摘要：

  We report the one-pot reactions of the 16e(-) half-sandwich complex CpCoS2C2B10H10 (1), methyl propiolate, and 3e(-)-donor ligands, which lead to selective B-functionalization at carborane with cyclopentadienyl as a functional group at ambient temperature in good yields. Metal-promoted activations of both a B-H bond of the carborane and a C-H bond of the Cp unit take place sequentially in the cooperation of organic ligands. The reaction requires a 3e(-)-donor ligand and an activated alkyne and is therefore suitable for a broad range of substrates. This investigation provides a simple and efficient synthetic route to B-functionalized carborane derivatives.

  DOI：

  10.1021/ja303334t

文献信息

• 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。
• Bond; Colton; Moir, Inorganic Chemistry, 1985, vol. 24, # 9, p. 1298 - 1302
  作者：Bond、Colton、Moir、Page

  DOI：——

  日期：——
• Barbier, Jean-Pierre; Ondo, Benjamin Mve; Hugel, Rene P., Journal of the Chemical Society, Dalton Transactions, 1985, p. 597 - 600
  作者：Barbier, Jean-Pierre、Ondo, Benjamin Mve、Hugel, Rene P.

  DOI：——

  日期：——
• Engelhardt, Lutz M.; Healy, Peter C.; Shephard, Robyn M., Inorganic Chemistry, 1988, vol. 27, # 13, p. 2371 - 2373
  作者：Engelhardt, Lutz M.、Healy, Peter C.、Shephard, Robyn M.、Skelton, Brian W.、White, Allan H.

  DOI：——

  日期：——