carbon monoxide;molybdenum;trichlorophosphane | 19212-18-1

• 分子结构分类: 无机化合物 - 混合金属/非金属化合物 - 过渡金属盐
• 英文名称: carbon monoxide;molybdenum;trichlorophosphane
• CAS: 19212-18-1
• 化学式: C₅Cl₃MoO₅P
• 分子量: 373.325
• InChiKey: VTQFQVRGUGASQP-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：

  carbon monoxide;molybdenum;trichlorophosphane 、 三正丁基氢锡 以 正戊烷 为溶剂， 以49%的产率得到(phosphane)pentacarbonylmolybdenum
  参考文献：
  名称：

  Nature of the Metal−Ligand Bond in M(CO)₅PX₃ Complexes (M = Cr, Mo, W; X = H, Me, F, Cl):  Synthesis, Molecular Structure, and Quantum-Chemical Calculations

  摘要：

  The syntheses of the phosphane complexes M(CO)(5)PH3 (M = MO, W), W(CO)(5)PD3, and W(CO)(5)PF3 and the results of X-ray structure analyses of W(CO)(5)PH3 and Mo(CO)(5)PCl3 are reported. Quantum-chemical DFT calculations of the geometries and M-P bond dissociation energies of M(CO)(5)PX3 (M = Cr, Mo, W; X = H, Me, F, Cl) have been carried out. There is no correlation between the bond lengths and bond dissociation energies of the M-P bonds. The PMe3 ligand forms the strongest and the longest M-P bonds of the phosphane ligands. The analysis of M-PX3 bonds shows that PCl3 is a poorer sigma donor and a stronger pi(P) acceptor than the other phosphanes. The energy decomposition analysis indicates that the M-P bonds of the PH3 and PMe3 complexes have a higher electrostatic than covalent character. The electrostatic contribution is between 56 and 66% of the total attractive interactions. The orbital interactions in the M-PH3 and M-PMe3 bonds have more sigma character (65-75%) than T character (25-35%). The M-P bonds of the halophosphane complexes M(CO)(5)PF3 and M(CO)(5)PCl3 are nearly half covalent and half electrostatic. The pi bonding contributes similar to50% to the total orbital interaction.

  DOI：

  10.1021/om020311d
• 作为产物：
  描述：

  molybdenum hexacarbonyl 在 PCl₃ 作用下， 以 甲基环己烷 为溶剂， 生成 carbon monoxide;molybdenum;trichlorophosphane
  参考文献：
  名称：

  M（CO）5PX3（M = Cr，Mo，W和X = F，Cl，Br）的紫外光电子（He I和He II）研究

  摘要：

  摘要给出了配合物M（CO）5PX3（M = Cr，Mo，W; X = F，Cl，Br）的He I和He II光谱。该分配基于与单独的PX3和M（CO）6分子的光谱的比较，这些光谱涉及谱带的位置以及从He I到He II的强度差。可以得出有关配合物中σ键和π键以及金属上电荷的结论。可以证明电离势与红外频率之间的相关性。

  DOI：

  10.1016/s0020-1693(00)87445-9

文献信息

• Diphosphor, phosphor-, arsen- und antimonatome als clusterbaugruppen
  作者：Heinrich Lang、Gottfried Huttner、Laszlo Zsolnai、Gerhard Mohr、Beate Sigwarth、Ute Weber、Olli Orama、Ibrahim Jibril

  DOI：10.1016/s0022-328x(00)99683-9

  日期：1986.4

  Reactions of Fe2(CO)9 with LnMPHal3 (LnM = 16-electron fragment: Cp(CO)2Mn, (CO)5Cr, (CO)5Mo, (CO)5W) yield clusters of the type F3(CO)9(μ4-P)2(MLn)2 (II). Compounds II contain the trigonal bipyramidal cluster framework Fe3(CO)9(μ3-P)2, the basis of which is a closed triangle formed by three Fe(CO)3 units; the apical positions of the trigonal bipyramid are occupied by phosphorus atoms. Each of the

  的Fe的反应2（CO）9的L Ñ MPHal 3（L Ñ M = 16电子片段：CP（CO）2的Mn，（CO）5的Cr，（CO）5沫，（CO）5 W）得到F型的簇3（CO）9（μ 4 -P）2（ML ñ）2（II）。化合物（II）包含三角双锥群集框架的Fe 3（CO）9（μ 3 -P）2，在此基础上的是由三个的Fe（CO）形成的闭合三角形3单位; 三角双锥的顶端位置被磷原子占据。每个封端的磷原子结合一个额外的ML n片段。类型II的化合物也被选自Fe得到2（CO）6（μ 3 -P）2（ML Ñ）2（I）由正式添加的Fe（CO）的3组。另一种一般合成方法来簇的Fe 3（CO）9（μ 4 -X）2（ML Ñ）2（X = P，砷，锑）是卤代亚膦，arsinidene或stibinidene络合物，（L的反应Ñ M）2具有Na 2 Fe（CO）4的XHal（X = P，As，Sb）。
• Noeth, Heinrich; Thorn, Volker, Zeitschrift fur Naturforschung, Teil B: Anorganische Chemie, Organische Chemie, 1981, vol. 36, # 11, p. 1424 - 1431
  作者：Noeth, Heinrich、Thorn, Volker

  DOI：——

  日期：——
• Scheer, M.; Gremler, St., Zeitschrift fur Anorganische und Allgemeine Chemie
  作者：Scheer, M.、Gremler, St.

  DOI：——

  日期：——
• 95Mo NMR Spectroscopic Evidence for the Weak .pi.-Acceptor Ability of PCl3
  作者：Elmer C. Alyea、Shuquan Song

  DOI：10.1021/ic00119a006

  日期：1995.7

  Stepwise-displaced molybdenum carbonyl complexes Mo(CO)(6-n)L(n) (n = 1-3) of chlorosubstituted phosphine ligands PPh(3-m)Cl(m), (m = 0-3) were prepared and studied by Mo-95, P-31, and C-13 NMR spectroscopies. The extremely deshielding influence of the PCl3 ligand (and related ligands) on the transition metal NMR chemical shift and the shielding trend on the P-31 NMR resonance position indicate that this putatively strong pi-acceptor is actually a weaker pi-acceptor than all other phosphorus Ligands employed (except for PBr3). This conclusion is consistent with C-13 NMR and IR spectroscopic results for all the complexes and is also in agreement with the known very weak bond strength of M-PCl3 in Mo and Ni carbonyl complexes as well as a theoretical calculation. The traditionally used infrared parameters for phosphine-substituted metal carbonyls are not suitable for evaluating the sigma- and pi characters of trans phosphorus ligands because both a weaker sigma-donor and a stronger pi-acceptor would lead to a high carbonyl vibrational frequency. The expectation of very short Mo-PCl3 and Mo-PBr3 bond distances (consistent with literature X-ray crystallographic results for a few related transition metal complexes), coupled with the evidence for the low pi-acceptor ability of these phosphorus ligands, leads to an unconventional conclusion: a weak sigma-donor may form a short M-P bond with weak bond strength in the absence of a pi-bonding contribution. It is also concluded that the P-31 NMR chemical shift, or coordination chemical shift Delta delta(P-31), can reflect the electronic and steric variations in Mo-P bonding: both pi- acid sigma-bonding will increase the Delta delta(P-31) by inducing a deshielding effect on the P-31 nucleus, while steric effects decrease the Delta delta(P-31) by inducing a shielding effect.