[Me2Si(C5Me4)2]MoH2 | 230315-83-0

• 英文名称: [Me2Si(C5Me4)2]MoH2
• CAS: 230315-83-0
• 化学式: C₂₀H₃₂MoSi
• 分子量: 396.5
• InChiKey: ISPFQNNPZLRQJR-UHFFFAOYSA-N

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：
  None

反应信息

• 作为反应物：
  描述：

  [Me2Si(C5Me4)2]MoH2 生成 (C5Me4Si(Me2)C5Me3CH2)MoH
  参考文献：
  名称：

  Churchill, David; Shin, Jun Ho; Hascall, Tony, Organometallics, 1999, vol. 18, p. 2403 - 2406

  摘要：

  DOI：
• 作为产物：
  描述：

  [Me2Si(C5Me4)2]MoCl2 、 lithium aluminium tetrahydride 生成 [Me2Si(C5Me4)2]MoH2
  参考文献：
  名称：

  Churchill, David; Shin, Jun Ho; Hascall, Tony, Organometallics, 1999, vol. 18, p. 2403 - 2406

  摘要：

  DOI：

文献信息

• Modeling Aspects of Hydrodesulfurization at Molybdenum:  Carbon−Sulfur Bond Cleavage of Thiophenes by <i>Ansa</i> Molybdenocene Complexes
  作者：David G. Churchill、Brian M. Bridgewater、Gerard Parkin

  DOI：10.1021/ja9936316

  日期：2000.1.1

  complexes, [Mesub 2}Si(Csub 5}Mesub 4})sub 2}]MoHsub 2} and [Mesub 2}Si(Csub 5}Mesub 4})sub 2}]Mo(Ph)H, exhibit reactivity that models required aspects of the mechanism for thiophene HDS. Thus, upon photolysis, [Mesub 2}Si(Csub 5}Mesub 4})sub 2}]MoHsub 2} is capable of inducing C -S bond cleavage of thiophene (T) to give [Mesub 2}Si(Csub 5}Mesub 4})sub 2}]Mo(mu}sup 2}-C,S-T). The

  加氢脱硫 (HDS) 是一种从原油原料和燃料中去除硫的方法，被认为是过渡金属的最大量和最重要的工业催化应用。在原油中存在的硫杂质中，噻吩是最能抵抗 HDS 的。因此，彻底了解噻吩对过渡金属中心的反应性对于改进现有的 HDS 技术至关重要。因此，作者被提示研究噻吩对钼配合物的反应性，以发现与 HDS 相关的钼化学。发现 ansa 钼茂络合物 [Mesub 2}Si(Csub 5}Mesub 4})sub 2}]MoHsub 2} 和​​ [Mesub 2}Si(Csub 5}Mesub 4})sub 2}]Mo(Ph)H，表现出反应性，模拟了噻吩 HDS 机制所需的方面。因此，在光解时，[Mesub 2}Si(Csub 5}Mesub 4})sub 2}]MoHsub 2} 能够诱导噻吩 (T) 的 C -S 键断裂，得到[Mesub 2}Si(Csub 5}Mesub
• Molybdenocene Trihydride Complexes:  Influence of a [Me₂Si] <i>Ansa</i> Bridge on Classical versus Nonclassical Nature, Stability with Respect to Elimination of Dihydrogen, and Acidity
  作者：Kevin E. Janak、Jun Ho Shin、Gerard Parkin

  DOI：10.1021/ja047554c

  日期：2004.10.1

  Experimental and computational studies on a series of cationic molybdenocene trihydride complexes, namely [Cp2MoH3](+), [(Cp-But)(2)MoH3](+), [Cp*2MoH3](+), and [Me2Si(C5Me4)(2)]MoH3}(+), demonstrate that the most stable form for the ansa molybdenocene derivative is a nonclassical dihydrogen-hydride isomer, [Me2Si(C5Me4)(2)]Mo(eta(2)-H-2)(H)}(+), whereas the stable forms for the non-ansa complexes are classical trihydrides, [Cp2Mo(H)(3)](+), [(CPBut)(2)Mo(H)(3)](+), and [Cp*Mo-2(H)(3)](+). In addition to altering the classical versus nonclassical nature of [Cp*2MoH3](+) and [Me2Si(C5Me4)(2)]Mo(eta(2)-H-2)(H)}(+), the [Me2Si] ansa bridge also markedly influences the stability of the complex with respect to elimination of H-2 and dissociation of H+. Finally, computational studies on [H2Si(C5H4)(2)]MoH2D}(+) and [H2Si(C5H4)(2)]MoHD2}(+) establish that deuterium exhibits a greater preference than hydrogen to occupy dihydrogen versus hydride sites.
• Carbon–hydrogen versus carbon–chalcogen bond cleavage of furan, thiophene and selenophene by ansa molybdenocene complexes
  作者：David G. Churchill、Brian M. Bridgewater、Guang Zhu、Keliang Pang、Gerard Parkin

  DOI：10.1016/j.poly.2005.08.016

  日期：2006.1

  [Me2Si(C5Me4)(2)]MoH2 reacts with furan and benzofuran to yield products resulting from C-H bond cleavage, namely [Me2Si(C5Me4)(2)]Mo(eta(1)-C-C4H3O)H and [Me2Si(C5Me4)(2)]Mo(eta(2)-C-C8H5O)H, whereas the corresponding reactions of selenophene and benzoselenophene yield products resulting from C-Se bond cleavage, namely [Me2Si(C5Me4)(2)]Mo(eta(2)-C,Se-SeC4H4) and [Me2Si(C5Me4)(2)]Mo(eta(2)-C,Se-SeC8H6). On this basis, the reactivity of the selenophene derivatives is analogous to that of previously reported thiophene derivatives, while the reactivity of the furan derivatives is unique. DFT calculations indicate that C-E (E = O, S, Se) bond cleavage is thermodynamically more favored than C-H bond cleavage for each of the chalcogen derivatives. As such, the calculations provide evidence that C-O bond cleavage of the furan derivatives is not observed because of kinetic factors. DFT calculations also demonstrate that the observation of C-S bond cleavage of thiophene by the ansa metallocene [Me2Si(C5Me4)(2)]MoH2 and C-H bond cleavage by Cp2MoH2 is dictated by thermodynamic factors. Specifically, the Me2Si ansa bridge thermodynamically favors [Me2Si(C5Me4)(2)]Mo(eta(2)-C,S-SC4H4) over [Me2Si(C5Me4)(2)]Mo(eta(1)-C-SC4H3)H because the bridge promotes a shift in the coordination of the cyclopentadienyl rings from eta(5)-coordination towards eta(3)-coordination and this thermodynamically unfavorable modification is stabilized by sulfur-to-metal pi-donation within [Me2Si(C5Me4)(2)]Mo(eta(2)-C,S-SC4H4). (c) 2005 Elsevier Ltd. All rights reserved.