tris(4,4',5,5'-tetramethyl-2,2'-biphosphinidene)molybdenum | 207611-49-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 磷环化合物
• 英文名称: tris(4,4',5,5'-tetramethyl-2,2'-biphosphinidene)molybdenum
• 英文别名: 2-(4,5-dimethylphosphinin-2-yl)-4,5-dimethylphosphinine;molybdenum
• CAS: 207611-49-2
• 化学式: C₄₂H₄₈MoP₆
• 分子量: 834.626
• InChiKey: IXOQFQUMQWMVPC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14.85
• 重原子数：
  49.0
• 可旋转键数：
  0.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  五氯化钼 、 4,4',5,5'-tetramethyl-2,2′-biphosphinine 在 Mg 作用下， 以 四氢呋喃 为溶剂， 以50%的产率得到tris(4,4',5,5'-tetramethyl-2,2'-biphosphinidene)molybdenum
  参考文献：
  名称：

  Synthesis, Unusual Trigonal Prismatic Geometry, and Theoretical Study of the Homoleptic Tris-(2,2‘-biphosphinine) Complexes of Chromium, Molybdenum, and Tungsten

  摘要：

  The preparation of homoleptic tris-(4,4',5,5'-tetramethyl-2,2'-biphosphinine) complexes of chromium 2, molybdenum 3, and tungsten 4 [M(tmbp)(3)] is described. These complexes can be obtained by the simple reduction of CrCl3. 3THF, MoCl5, and WCl6, respectively, with magnesium in the presence of the ligand. The tungsten complex 4 was alternatively prepared in better yields by the reduction of the [WBr4(MeCN)(2)] complex with zinc dust. The structure of 4 has been unambiguously confirmed by an X-ray crystal structure analysis. Surprisingly, whereas an octahedral geometry (theta = 60 degrees) would have been expected for a d(6) ML6, complex 4 presents a nearly trigonal prismatic structure (theta = 15 degrees). Two data reveal that a significant electronic transfer from the metal to the ligand occurs: short P-W bond distances (2.35-2.36 Angstrom) and a shortened C-C bridge (1.442(4) Angstrom) between two phosphinine subunits. Ab initio calculations at the DFT(B3LYP) level have been undertaken to rationalize this deviation from the ideal octahedral geometry. The geometry of [W(P2C2H4)(3)], which was chosen as a model for 4, and that of the d(0) ML6 tris-(dithiolene) complex [W(S2C2H4)(3)], which is known to be trigonal prismatic, have been calculated. In both cases the calculated geometries are in good agreement with the corresponding observed data. On the basis of these results it is suggested that [W(P2C2H4)(3)] can be most conveniently described as a fully oxidized d(0) complex in which the phosphorus P lone pairs are conjugated to the C=C double bond and not bonded to the metal center.

  DOI：

  10.1021/ic980042c