(η5-pentaethylcyclopentadienyl)molybdenum(IV)H3(1,2-(diphenylphosphino)ethane) | 265122-96-1

• 英文名称: (η5-pentaethylcyclopentadienyl)molybdenum(IV)H3(1,2-(diphenylphosphino)ethane)
• 英文别名: (η5-pentaethylcyclopentadienyl)tris(hydrido)(1,2-bis(diphenylphosphino)ethane)molybdenum
• CAS: 265122-96-1
• 化学式: C₄₁H₅₂MoP₂
• 分子量: 702.751
• InChiKey: HRKRXQGLQUOCEC-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：

  四氟硼酸-二乙醚络合物 、 (η5-pentaethylcyclopentadienyl)molybdenum(IV)H3(1,2-(diphenylphosphino)ethane) 以 乙醚 为溶剂， 以64%的产率得到[(η5-pentaethylcyclopentadienyl)MoH4(1,2-(diphenylphosphino)ethane)][BF4]
  参考文献：
  名称：

  Protonation and oxidation chemistry of a pentaethylcyclopentadienyl-containing molybdenum(IV) trihydride complex

  摘要：

  Compound (CpMoCl4)-Mo-Et (Cp-Et= eta(5)-C5Et5) (1) can be transformed into (CpMoH3)-Mo-Et(dppe) (2) and (CpMoD3)-Mo-Et(dppe) (2-d(3)) [dppe = 1,2-(diphenylphosphino)ethane] by reaction with LiAlX4 (X = H and D, respectively). The protonation and oxidation studies of these two compounds, in comparison with previously reported studies on (C5Me5) analogs, show important differences that may be attributed to a kinetic stabilization of the products, which is steric in nature. Protonation of 2 with HBF, in acetonitrile affords [(CpMoH4)-Mo-Et(dppe)](+) (3), which only slowly decomposes to [(CpMoH2)-Mo-Et(MeCN)(dppe)](+) (4). Further protonation of the latter affords the monohydride species [Cp*MoH(dppe)(MeCN)(2)](2+) in three different forms, 5-7. Direct protonation of 2 with 2 equiv, of HBF, shows the formation of all of the above compounds, plus a new compound, [(CpMoH3)-Mo-Et(dppe)(MeCN)](2+) (8), to which a classical structure is assigned. The protonation of 2-d(3) indicates reversibility for the proton transfer processes. The oxidation of 2 in MeCN affords [2](+), which decomposes slowly in MeCN to afford a mixture of 4 and 5 as major products. No compound 8, on the other hand, is obtained by oxidation of 2, neither with 1 nor with 2 equiv. of oxidizing agent. Mechanistic schemes that rationalize all these observations are proposed. (C) 2000 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0020-1693(99)00584-8
• 作为产物：
  描述：

  1,2-双(二苯基膦)乙烷 、 (η5-pentaethylcyclopentadienyl)MoCl4 、 lithium aluminium tetrahydride 在 甲醇 作用下， 以 乙醚 、 甲苯 为溶剂， 以82%的产率得到(η5-pentaethylcyclopentadienyl)molybdenum(IV)H3(1,2-(diphenylphosphino)ethane)
  参考文献：
  名称：

  Protonation and oxidation chemistry of a pentaethylcyclopentadienyl-containing molybdenum(IV) trihydride complex

  摘要：

  Compound (CpMoCl4)-Mo-Et (Cp-Et= eta(5)-C5Et5) (1) can be transformed into (CpMoH3)-Mo-Et(dppe) (2) and (CpMoD3)-Mo-Et(dppe) (2-d(3)) [dppe = 1,2-(diphenylphosphino)ethane] by reaction with LiAlX4 (X = H and D, respectively). The protonation and oxidation studies of these two compounds, in comparison with previously reported studies on (C5Me5) analogs, show important differences that may be attributed to a kinetic stabilization of the products, which is steric in nature. Protonation of 2 with HBF, in acetonitrile affords [(CpMoH4)-Mo-Et(dppe)](+) (3), which only slowly decomposes to [(CpMoH2)-Mo-Et(MeCN)(dppe)](+) (4). Further protonation of the latter affords the monohydride species [Cp*MoH(dppe)(MeCN)(2)](2+) in three different forms, 5-7. Direct protonation of 2 with 2 equiv, of HBF, shows the formation of all of the above compounds, plus a new compound, [(CpMoH3)-Mo-Et(dppe)(MeCN)](2+) (8), to which a classical structure is assigned. The protonation of 2-d(3) indicates reversibility for the proton transfer processes. The oxidation of 2 in MeCN affords [2](+), which decomposes slowly in MeCN to afford a mixture of 4 and 5 as major products. No compound 8, on the other hand, is obtained by oxidation of 2, neither with 1 nor with 2 equiv. of oxidizing agent. Mechanistic schemes that rationalize all these observations are proposed. (C) 2000 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0020-1693(99)00584-8

文献信息

• Preparation and structure of the 17-electron (η5-C5R5)Mo(OH)2(dppe) (R=Me, Et) organometallic compounds containing two gem-terminal hydroxide ligands
  作者：Dolores Morales、Brett Pleune、Rinaldo Poli、Philippe Richard

  DOI：10.1016/s0022-328x(99)00539-2

  日期：2000.2

  Oxidation of (eta(5)-C5R5)MoH3(dppe) (R = Me, Et) by Cp2Fe+ in wet THF leads to the formation of the corresponding (eta(5)-C5R5)Mo(OH)(2)(dppe). These compounds show a low-potential reversible oxidation wave. The structure of the C5Et5 complex has been confirmed by X-ray diffraction methods: triclinic; space group ; a =11.030(1); b = 12.533(1); c = 16.241 (1) Angstrom; alpha = 68.585(7); beta = 75.197(5); gamma = 83.991(7)degrees; V = 2020.6(3) Angstrom(3); Z = 2; D-calc = 1.324 g cm(-3), mu(Mo-K-alpha) = 0.441 mm(-1); R-1 = 0.0325; wR(2) = 0.0875 for 415 parameters and 6823 independent reflections [R-int = 0.0177] with I = 2 sigma(I). The molecule shows a four-legged piano-stool geometry with two terminal OH ligands in a relative trans configuration. The complex EPR properties indicate that an equilibrium mixture of various species is present in solution. (C) 2000 Elsevier Science S.A. All rights reserved.