cis,trans-H2Rh(PMe3)3Cl | 144241-92-9

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: cis,trans-H2Rh(PMe3)3Cl
• 英文别名: cis-mer-[RhH2Cl(PMe3)3]；chloro(dihydrido)rhodium;trimethylphosphane
• CAS: 144241-92-9；857076-25-6；857076-27-8
• 化学式: C₉H₂₉ClP₃Rh
• 分子量: 368.609
• InChiKey: XGFQXNIXVFVBQF-UHFFFAOYSA-M

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

• 作为产物：
  描述：

  氢气 、 三甲基膦 、 氯羰基双(三甲基膦)铑(I) 以 氘代苯 为溶剂， 生成 cis,trans-H2Rh(PMe3)3Cl
  参考文献：
  名称：

  Activation of H₂by chlorocarbonylbis(trimethylphosphine)rhodium(I) labilizes CO and produces the new binuclear complex H(Cl)Rh(PMe₃)₂(µ-H)(µ-Cl)RH(PMe₃)(CO)

  摘要：

  利用核磁共振波谱与对位富集氢对[RhCl(CO)(PMe3)2]中 H2 的氧化加成进行了跟踪研究，结果表明 CO 发生了唇化并形成了一种不寻常的双核复合物。

  DOI：

  10.1039/c39930001185

文献信息

• Transfer-dehydrogenation of alkanes catalyzed by rhodium(I) phosphine complexes
  作者：Kun Wang、Martin E. Goldman、Thomas J. Emge、Alan S. Goldman

  DOI：10.1016/0022-328x(96)06116-5

  日期：1996.7

  much greater temperatures. Analogs with halides other than chloride (Br, I), or with pseudo-halides (OCN, N3), are found to exhibit generally similar behavior: high catalytic activity under H2 and measurable but much lower activity in the absence of H2. Thermolysis (under argon) of complexes [RhL2Cl]n (n = 1, 2; L is a phosphine bulkier than PMe3) in cyclooctane in the absence of hydrogen acceptors yielded

  以前已报道过Rh（PMe 3）2 ClL'（L'= CO或三取代的膦）和[Rh（PMe 3）2 Cl] 2形式的配合物可使用烯烃氢受体在二氢气氛。据报道，在没有H 2的情况下，即使在更高的温度下，这种配合物也能实现转移-脱氢，但速率和总催化转化率要低得多。发现与氯化物以外的卤化物（Br，I）或假卤化物（OCN，N 3）的类似物表现出大致相似的行为：在H 2下具有高催化活性和在没有H 2的情况下可测量但活性低得多。在不存在氢受体的情况下，在环辛烷中热解（在氩气下）配合物[RhL 2 Cl] n（n = 1，2； L是比PMe 3更大的膦），生成环辛烯。然而，转移-脱氢受到配体分解的困扰。在氢气氛下，含有比PMe 3体积大得多的配体的络合物不影响脱氢作用。具有三齿配体的络合物，（η 3 -PXP）RHL'（PXP =（ME 2 PCH 2我2 Si）的2 N，我2 PCH 2（2,6-C 6 H
• Dalton communications. Rapid characterisation of rhodium dihydrides by nuclear magnetic resonance spectroscopy using indirect two-dimensional methods and para-hydrogen
  作者：Simon B. Duckett、Graham K. Barlow、Martin G. Partridge、Barbara A. Messerle

  DOI：10.1039/dt9950003427

  日期：——

  When [RhH2(PMe(3))(3)Cl], incorporating chemically inequivalent hydrides, and [RhH2(PMe(3))(4)]Cl, containing magnetically inequivalent hydrides.,were generated using para-enriched hydrogen, their H-1-Rh-103 and H-1-P-31 two-dimensional NMR spectra were quickly obtained from < 1 mg of complex with and without the aid of pulsed field gradients.
• Messerle, Barbara A.; Sleigh, Christopher J.; Partridge, Martin G., Journal of the Chemical Society, Dalton Transactions, 1999, # 5, p. 1429 - 1436
  作者：Messerle, Barbara A.、Sleigh, Christopher J.、Partridge, Martin G.、Duckett, Simon B.

  DOI：——

  日期：——
• In Situ NMR Observation of Mono- and Binuclear Rhodium Dihydride Complexes Using Parahydrogen-Induced Polarization
  作者：Andreas Koch、Joachim Bargon

  DOI：10.1021/ic991319r

  日期：2001.1.1

  Starting from the binuclear complex [RhCl(NBD)](2) (NBD = 2,5-norbornadiene) in the presence of the phosphines L = PMe3, PMe2Ph, PMePh2, PEt3, PEt2Ph, PEtPh2, or P(n-butyl)(3), various mononuclear dihydrides of the type Rh(H)(2)ClL3, i.e., those of the homogeneous hydrogenation catalysts RhClL3, have been obtained upon addition of parahydrogen, and their H-1 NMR spectra have been investigated using parahydrogen-induced polarization (PHIP). Furthermore, the two binuclear complexes (H)(Cl)Rh(PMe3)(2)(mu -Cl)(mu -H)Rh(PMe3) and (H)(CI)Rh(PMe2Ph)(2)(mu -Cl)(mu -H)Rh(PMe2Ph) have been detected and characterized by means of this in situ NMR method. Analogous complexes with trifluoroacetate instead of chloride, i.e., Rh(H)(2)(CF3COO)L-3, have been generated in situ starting from Rh(NBD)(acac) in the presence of trifluoroacetic acid in combination with the phosphines L = PPh3, PEt2Ph, FEB, and P(n-butyl)(3), and their H-1 NMR parameters have been determined.