Mo(CO)(η2-silane)(depe)2 | 160260-48-0

• 英文名称: Mo(CO)(η2-silane)(depe)2
• CAS: 160260-48-0
• 化学式: C₂₁H₅₂MoOP₄Si
• 分子量: 568.564
• InChiKey: MBYQSZWKCFQBNJ-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

• 作为产物：
  描述：

  硅烷 、 [Mo(CO)(depe)2]2(μ-N2) 以 甲苯 为溶剂， 以59%的产率得到Mo(CO)(η2-silane)(depe)2
  参考文献：
  名称：

  Experimental and Theoretical Studies of Bonding and Oxidative Addition of Germanes and Silanes, EH_4-nPh_n (E = Si, Ge; n = 0−3), to Mo(CO)(diphosphine)₂. The First Structurally Characterized Germane σ Complex

  摘要：

  Reaction of GeH4 and GeH3Ph with the agostic complex Mo(CO)(dppe)(2) (dppe = Ph2PC2H4PPh2) provides germane sigma complexes Mo(CO)(eta(2) -GeH4-nPhn)(dppe)(2) (n = 0, 1). The coordination in these complexes has been assigned as (eta(2) -Ge-H) on the basis of NMR and IR spectroscopy and by comparison to the analogous complexes of silanes. When the more electron-rich phosphine depe (depe = Et2PC2H4PEt2) is used, oxidative addition (OA) products MoH(GeH3)(CO)(depe)(2) and MoH(GeH2Ph)(CO)(depe)(2) are isolated (NMR and X-ray evidence). However, when the secondary organogermane GeH2Ph2 is used in the depe system, the eta(2)-complex Mo(CO)(eta(2)-GeH2Ph2)(depe)(2) is obtained. This complex was characterized by X-ray crystallography and NMR and IR spectroscopy. The Mo(CO)(eta(2)-GeH3Ph)(dppe)(2) and MO(CO)(eta(2)-GeH2Ph2)(depe)(2) complexes were found to be in tautomeric equilibrium with their OA products in solution. Structure and bonding comparisons are made to the analogous silane complexes, e.g., Mo(CO)(eta(2) -SiH2Ph2)(depe)(2), the X-ray structure for which is also reported. The Ge-H bonds undergo OA much more easily than Si-H, and to obtain further insight into the activation processes, ab initio DFT calculations have been performed on Mo(CO)(EH(4-n)vin(n))(dhpe)(2) model complexes (E = Si, Ge; n = 0-3; dhpe = H2PCH2CH2PH2; vin = CH=CH2) and also the analogous H-2 complex. Because the ease of the whole OA process is a balance between the E-H bonding energy and Mo-E bonding energy, it can be concluded that the factor that makes OA of the Ge-H bond easier than that for Si-H is the relative weakness of the Ge-H bond, despite the fact that the Mo-Ge bond is also weaker. This competition between both factors is also seen for OA of H-2, for which although the Mo-H bonding energy is much higher than Mo-Si and Mo-Ge bonding energies, the H-H bond is also significantly stronger than the Si-H and Ge-H bonds. In general, the ease of OA of molecular hydrogen is between that of germanes and silanes. Calculations show that for alkanes the OA is much more difficult because the loss of the high C-H bond energy (comparable to or greater than that for H-H) is not as well compensated for by the energy of formation of the Mo-C bond due to the weakness of the Mo-C bond.

  DOI：

  10.1021/om030569j

文献信息

• Luo, Xiao-Liang; Kubas, Gregory J.; Burns, Carol J., Journal of the American Chemical Society, 1995, vol. 117, # 3, p. 1159 - 1160
  作者：Luo, Xiao-Liang、Kubas, Gregory J.、Burns, Carol J.、Bryan, Jeffrey C.、Unkefer, Clifford J.

  DOI：——

  日期：——