[(pentamethylcyclopentadienide)2Co][OTf] | 952128-76-6

• 英文名称: [(pentamethylcyclopentadienide)2Co][OTf]
• 英文别名: [Cp*₂Co][OTf]；[(pentamethylcyclopentadienide)₂Co][OTf]；[(C5Me5)2Co(III)][OTf]
• CAS: 952128-76-6
• 化学式: CF₃O₃S*C₂₀H₃₀Co
• 分子量: 478.522
• InChiKey: ZPPKUEXBNLXVCD-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：
  None
• 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：

  、 silver trifluoromethanesulfonate 以 丙酮 为溶剂， 以89%的产率得到[(pentamethylcyclopentadienide)2Co][OTf]
  参考文献：
  名称：

  十甲基二茂铁鎓盐与全氟烷基磺酸盐和-羧酸盐阴离子的相变和热性质表现出无序性

  摘要：

  十甲基二茂铁鎓盐与全氟烷基磺酸根阴离子（C。ñF。2个ñ+1个所以第三名--; n  = 1、4和8）和全氟烷基羧酸根阴离子（C。ñF。2个ñ+1个一氧化碳2个--; n  = 1-4）用于研究阴离子对盐的热行为的影响。差示扫描量热法（DSC）测量表明，所有盐在固态下均表现出相变。具有八甲基二茂铁鎓阳离子或十甲基钴co鎓阳离子的盐表现出与相应的十甲基二茂铁鎓盐不同的相序。用结晶学方法研究了两种盐与相变有关的结构变化。[Fe（C 5 Me 5）2 ]（CF 3 SO 3）在-121.6°C时伴随着阳离子构象以不同比例排列为偏影和交错构象的顺序。在低温阶段，单位晶胞体积变大六倍，并且空间群从P mn2 1变为P 1。[Fe（C 5 Me 5）2 ]（C 3 F 7 CO 2）在-115°C时的相变不伴随晶胞或空间群（P 2 1 / c）。在低温相中，存在于高温相中的阴离子的释放或位移被抑制，这

  DOI：

  10.1016/j.jorganchem.2012.04.005

文献信息

• The dramatic acceleration effect of imidazolium ionic liquids on electron transfer reactions
  作者：Doo Seong Choi、Dong Hyun Kim、Ueon Sang Shin、Ravindra R. Deshmukh、Sang-gi Lee、Choong Eui Song

  DOI：10.1039/b708044a

  日期：——

  Imidazolium ionic liquids (ILs) exhibited a dramatic acceleration effect on the electron transfer from metal complexes such as (C(5)Me(5))(2)Fe(II) and (C(5)Me(5))(2)Co(II) to the oxygen molecule; this acceleration effect can be ascribed to the stabilization of the oxygen radical anions by coordinating with the acidic C2-H of imidazolium ILs.

  咪唑离子液体（ILs）对金属络合物如（C（5）Me（5））（2）Fe（II）和（C（5）Me（5））（2 ）Co（II）到氧分子; 这种加速作用可以归因于通过与咪唑类ILs的酸性C2-H配合来稳定氧自由基阴离子。
• Quantifying the Electron Donor and Acceptor Abilities of the Ketimide Ligands in M(N═C^<i>t</i>Bu₂)₄ (M = V, Nb, Ta)
  作者：Peter L. Damon、Cameron J. Liss、Richard A. Lewis、Simona Morochnik、David E. Szpunar、Joshua Telser、Trevor W. Hayton

  DOI：10.1021/acs.inorgchem.5b02017

  日期：2015.10.19

  Addition of 4 equiv of Li(N=(CBu2)-Bu-t) to VCl3 in THF, followed by addition of 0.5 equiv of 12, generates the homoleptic V(IV) ketimide complex, V(N=(CBu2)-Bu-t)(4) (1), in 42% yield. Similarly, reaction of 4 equiv of Li(N=(CBu2)-Bu-t) with NbCl4(THF)(2) in THF affords the homoleptic Nb(IV) ketimide complex, Nb(N=(CBu2)-Bu-t)(4) (2), in 55% yield. Seeking to extend the series to the tantalum congener, a new Ta(IV) starting material, TaCl4(TMEDA) (3), was prepared via reduction of TaCl5 with Et3SiH, followed by addition of TMEDA. Reaction of 3 with 4 equiv of Li(N=(CBu2)-Bu-t) in THF results in the isolation of a Ta(V) ketimide complex, Ta(Cl)(N=(CBu2)-Bu-t)(4) (5), which can be isolated in 32% yield. Reaction of 5 with Tl(OTf) yields Ta(OTf) (N=(CBu2)-Bu-t)(4) (6) in 44% yield. Subsequent reduction of 6 with Cp*Co-2 in toluene generates the homoleptic Ta(IV) congener Ta(N=(CBu2)-Bu-t)(4) (7), although the yields are poor. All three homoleptic group 5 ketimide complexes exhibit squashed tetrahedral geometries in the solid state, as determined by X-ray crystallography. This geometry leads to a d(x2-y2)(1) (B-2(1) in D-2d) ground state, as supported by DFT calculations. EPR spectroscopic analysis of 1 and 2, performed at X- and Qband frequencies (similar to 9 and 35 GHz, respectively), further supports the B-2(1) ground-state assignment, whereas comparison of 1, 2, and 7 with related group 5 tetra(ary1), tetra(amido), and tetra(alkoxo) complexes shows a higher M-L covalency in the ketimide-metal interaction. In addition, a ligand field analysis of 1 and 2 demonstrates that the ketimide ligand is both a strong a-donor and strong a-acceptor, an unusual combination found in very few organometallic ligands.