(η5-cyclopentadienyl)Co(1,2-dicarba-closo-dodecaborane-1,2-dithiolate) | 234756-09-3

• 英文名称: (η5-cyclopentadienyl)Co(1,2-dicarba-closo-dodecaborane-1,2-dithiolate)
• 英文别名: (η(5)-C5H5)Co(η(2)-S2C2B10H10)；(η⁵-cyclopentadienyl)Co(1,2-dicarba-closo-dodecaborane-1,2-dithiolate)；[cyclopentadienylCo(S₂C₂B₁₀H₁₀)]；[(cyclopentadienyl)cobalt(1,2-dicarba-closo-dodecaborane-1,2-dithiolato)]；[CpCo(S₂C₂B₁₀H₁₀)]；CpCo(S₂C₂B₁₀H₁₀)；CpCoS₂C₂B₁₀H₁₀
• CAS: 234756-09-3
• 化学式: C₇H₁₅B₁₀CoS₂
• 分子量: 330.431
• InChiKey: DZKIBBVZDXGIGR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (η5-cyclopentadienyl)Co(1,2-dicarba-closo-dodecaborane-1,2-dithiolate) 在 (CH₃)2CHCOOH or C₈H₇NO 作用下， 以 二氯甲烷 为溶剂， 生成 Co(C5H4B10H9C2(S)SCHCH2COOMe)
  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
• 作为产物：
  描述：

  carbonyl(η-5-cyclopentadienyl)diiodocobalt(III) 、 lithium 1,2-dicarba-closo-dodecaborane (12)-1,2-dithiolate 以 四氢呋喃 为溶剂， 以83%的产率得到(η5-cyclopentadienyl)Co(1,2-dicarba-closo-dodecaborane-1,2-dithiolate)
  参考文献：
  名称：

  小说单核二硫的加成反应ø -carboranylcobalt（III）配合物（η 5 -C 5 H ^ 5）的Co（η 2 -S 2 c ^ 2乙10 ħ 10）

  摘要：

  通过CpCo（CO）I 2与二硫代邻碳硼烷二锂Li 2反应获得单核16电子二硫代邻碳硼烷基钴（III）配合物CpCo（S 2 C 2 B 10 H 10）（2）。[S 2 C 2 B 10 H 10 ]（1）。配合物2与多种底物（例如CpCo（C 2 H 2）2，炔烃和重氮烷烃）反应，生成一类新的二硫代邻苯二酚。-结合有CpCo单元和烯烃和亚烷基配体的-碳硼烷基钴（III）化合物。

  DOI：

  10.1021/om990269v

文献信息

• Investigation into the reactivity of 16-electron complexes Cp^#Co(S₂C₂B₁₀H₁₀) (Cp^# = Cp, Cp*) towards methyl diazoacetate and toluenesulphonyl azide
  作者：Wei Zhong、Mingshi Xie、Yizhi Li、Hong Yan

  DOI：10.1039/c4ra13017k

  日期：——

  A three-component reaction of the 16-electron half-sandwich complex Cp*Co(S₂C₂B₁₀H₁₀) (2) with both methyl diazoacetate (MDA) and toluenesulphonyl azide (TsN₃) led to the formation of complexes 3 and 4, while a two-component reaction of complex 2 with MDA afforded products 5–7.

  一个由16电子半夹心配合物Cp*Co(S₂C₂B₁₀H₁₀) (2) 与甲基重氮乙酸酯(MDA)和对甲苯磺酰叠氮化合物(TsN₃)发生的三组分反应导致了配合物3和4的形成，而配合物2与MDA的两组分反应产生了产物5-7。
• Investigation of New Coordination Modes for Coordinatively Unsaturated (Dithiolato)cobalt(III) Complex [(<i>η</i>⁵-Cp)Co(1,2-S₂C₂B₁₀H₁₀-<i>S,S</i><i>‘</i>)]
  作者：Jae-Hong Won、Dae-Hyun Kim、Bo Young Kim、Sung-Joon Kim、Chongmok Lee、Sungil Cho、Jaejung Ko、Sang Ook Kang

  DOI：10.1021/om010892r

  日期：2002.4.1

  Cp-cobalt(III)-dithiolate complex of the general formula [(η5-Cp)Co(CabS,S‘)] (2) (CabS,S‘ = 1,2-S2C2B10H10-S,S‘) has been prepared by treatment of CpCo(CO)I2 with the corresponding dilithium dithiolato ligand Li2CabS,S‘(1). Experiments aimed at the characterization of new coordination modes for 2 are described. The reaction of 2 with BH3·THF produces an unexpected bimetallic cobalt dithiolate complex, [((η5-Cp)Co)2(CabS

  的单核16电子的Cp钴（III）络合物-dithiolate通式[（η 5 -Cp）的Co（驾驶室S，S'）]（2）（Cab S，S'通过用相应的二硫代二硫代锂配体Li 2 Cab S，S处理CpCo（CO）I 2制备1,2-S 2 C 2 B 10 H 10 - S，S '）。'（1）。旨在为新的协调模式的表征实验2中描述。的反应2用BH 3 ·THF产生意想不到的双金属钴二硫醇络合物，[（（η 5 -Cp）有限公司）2（驾驶室S，S'）]（3）。对于第二个新键合方式2是由治疗产生的2与路易斯碱（L），得到[（η 5 -Cp）的Co（驾驶室S，S'）（L）]（L = CNBu t（4a），PEt 3（4b）），其18电子物种由通过核Co-L键配位的单核2组成。对于第三个新键合方式2由[（图示η 5 -Cp）的Co（驾驶室S，S'）（η 1 -CH 2森达3 -小号）]（5）。2与（三甲基
• 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。
• Cobalt-Mediated B−H Activation and Cyclopentadienyl-Participated Diels−Alder Addition in the Reaction of a 16e CpCo Complex Containing an <i>o</i>-Carborane-1,2-dithiolato Ligand with HC≡C−C(O)Ph
  作者：Yuguang Li、Qibai Jiang、Yizhi Li、Hong Yan、Vladimir I. Bregadze

  DOI：10.1021/ic901970b

  日期：2010.1.4

  The reaction of the 16e half-sandwich complex CpCo(S2C2B10H10) (1) with HC≡C−C(O)Ph leads to a 17e complex 2 containing a bicyclo[2.2.1]heptene unit at the B3/B6 site of carborane. In the presence of air, water and silica 2 converts to two 16e complexes, 3 and 4, bearing new types of functionalized groups.

  16e半三明治复合物CpCo（S 2 C 2 B 10 H 10）（1）与HC≡C-C（O）Ph的反应导致在17e处含有双环[2.2.1]庚烯单元的17e络合物2碳硼烷的B3 / B6位点。在空气中，水和二氧化硅2转化为两个带有新型官能团的16e配合物3和4。