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.
• U.V. photoelectron (He I and He II) studies of M(CO)5PX3 (M = Cr, Mo, W and X = F, Cl, Br)
  作者：H. Daamen、G. Boxhoorn、A. Oskam

  DOI：10.1016/s0020-1693(00)87445-9

  日期：1978.1

  Abstract The He I and He II spectra of the complexes M(CO)5PX3 (M = Cr, Mo, W; X = F, Cl, Br) are presented. The assignment was based on the comparison with the spectra of the separate PX3 and M(CO)6 molecules concerning the positions of the bands and the intensity differences in going from He I to He II. Conclusions about the σ- and π-bonding in the complexes and about charge on the metals could be

  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。