(Cl)2Re(trimethylphosphine)2(NO)(acetonitrile) | 305811-60-3

• 英文名称: (Cl)2Re(trimethylphosphine)2(NO)(acetonitrile)
• CAS: 305811-60-3
• 化学式: C₈H₂₁Cl₂N₂OP₂Re
• 分子量: 480.328
• InChiKey: RZRNNFFSUFMLPG-UHFFFAOYSA-L

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

• 作为反应物：
  描述：

  (Cl)2Re(trimethylphosphine)2(NO)(acetonitrile) 、 sodium tetrahydroborate 以 四氢呋喃 为溶剂， 生成 ReH[(μ-H)B(H)2NC(H)(methyl](trimethylphosphine)2NO
  参考文献：
  名称：

  Borohydride reduction of a rhenium-bound acetonitrile: an example of a chelating iminoborane ligand at a low valent metal center

  摘要：

  The reduction of acetonitrile by [BU4N]BH4 at the rhenium(I) metal center in ReCl2(PMe3)(2)(CH3CN)NO to afford ReCl{(muH)B(H)(2)N=C(H)Me}(PMe3)(2)NO (2) is reported. The coordinated immoborane moiety is an intermediate in acetonitrile reduction. A mechanism is proposed for its formation. Further reaction with a hydride source (LiBH4, NaBH4, LiHBEt3) results in replacement of chloride with hydride to give ReH{(mu-H)B(H)(2)N=C(H)Mel}PMe3)(2)NO (3), together with varying proportions of ReH2(PMe3)(3)NO (4). Compounds 2 and 3 have been characterized by NMR and infrared data. The structure of 3 has additionally been elucidated by a single crystal X-ray diffraction study. Crystal data: C8H26BN2OP2Re, triclinic, P (1) over bar, a = 8.821(7) Angstrom, b = 12.4062(11) Angstrom, c = 15.5822(12) Angstrom, alpha = 70.004(9)degrees, beta = 82.726(9)degrees, Z = 4, R = 0.0535, R-w = 0.1325. The H-b/H-t hydrogen exchange process in the iminoborane moiety of 2 and 3 has been studied by NMR spectroscopy and a negative value of DeltaS(#) found for this process. The proposed mechanism for this exchange resembles that of P-hydrogen elimination in metal alkyls. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(02)02165-4
• 作为产物：
  描述：

  乙腈 、 在 trimethylamine N-oxide 作用下， 以 乙腈 为溶剂， 以94%的产率得到(Cl)2Re(trimethylphosphine)2(NO)(acetonitrile)
  参考文献：
  名称：

  Remarkable low symmetry hydrogen bonding network in the structure of ReCl2(NCMe)(NO)(PMe3)2

  摘要：

  The title compound 1 crystallizes in the space group P2(1)/a with Z = 44, being the largest Z value for a transition metal complex observed up to now. Responsible for the unusual high number of independent molecules in the asymmetric unit is a dense network of hydrogen bonds, which do not follow the general rule of lowest entropy in crystals. Methyl groups serve exclusively as H donor groups, leading to hydrogen bonds of the type C-H ... O and C-H ... Cl. The putative appearance of bond-stretch isomers within one single crystal could be traced to a hidden disorder phenomenon. Density functional calculations provided further evidence for this conclusion. (C) 2000 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0020-1693(00)00163-8