Mo(py)(CO)3(P(i)Pr3)2 | 927888-54-8

• 英文名称: Mo(py)(CO)3(P(i)Pr3)2
• 英文别名: mer,trans-Mo(CO)3(pyridine)(P(CH(CH3)2)3)2；Mo(P(i)Pr3)2(CO)3(pyridine)；Mo(P(i)Pr3)2(CO)3(py)
• CAS: 927888-54-8
• 化学式: C₂₆H₄₇MoNO₃P₂
• 分子量: 579.552
• InChiKey: AXBBTNZYUAQDHE-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：

  Mo(py)(CO)3(P(i)Pr3)2 、 1-异氰基金刚烷 以 甲苯 为溶剂， 以99%的产率得到Mo(P(i)Pr3)2(CO)3(1-adamantyl isocyanide)
  参考文献：
  名称：

  Experimental and Computational Studies of Binding of Dinitrogen, Nitriles, Azides, Diazoalkanes, Pyridine, and Pyrazines to M(PR₃)₂(CO)₃ (M = Mo, W; R = Me, ⁱPr).

  摘要：

  The enthalpies of binding of a number of N-donor ligands to the complex Mo((PPr3)-Pr-i)(2)(CO)(3) in toluene have been determined by solution calorimetry and equilibrium measurements. The measured binding enthalpies span a range of similar to 10 kcal mol(-1): Delta H-binding=-8.8 +/- 11.2 (N-2-Mo((PPr3)-Pr-i)(2)(CO)(3)); -10.3 +/- 0.8 (N-2); -11.2 +/- 0.4 (AdN(3) (Ad=1-adamantyl)); -13.8 +/- 0.5(N2CHSiMe3); -14.9 +/- 0.9 (pyrazine=pz); -14.8 +/- 0.6 (2,6-Me(2)PZ); -15.5 +/- 1.8 (Me2NCN); -16.6 +/- 0.4 (CH3CN); -17.0 +/- 0.4 (pyridine); -17.5 +/- 0.8 ([4-CH(3)pz][PF6] (in tetrahydrofuran)); -17.6 +/- 0.4 (C6H5CN); -18.6 +/- 1.8 (N2CHC (=O)OEt); and -19.3 +/- 2.5 kcal mol(-1) (pz)Mo((PPr3)-Pr-i)(2)(CO)(3)). The value for the isonitrile AdNC (-29.0 +/- 0.3) is 12.3 kcal mol(-1) more exothermic than that of the nitrile AdCN (-16.7 +/- 0.6 kcal mol(-1)). The enthalpies of binding of a range of arene nitrile ligands were also studied, and remarkably, most nitrile complexes were clustered within a 1 kcal mol(-1) range despite dramatic color changes and variation of v(CN). Computed structural and spectroscopic parameters for the complexes Mo ((PPr3)-Pr-i)(2)(CO)(3)L are in good agreement with experimental data. Computed binding enthalpies for Mo((PPr3)-Pr-i)(2)(CO)(3)L exhibit considerable scatter and are generally smaller compared to the experimental values, but relative agreement is reasonable. Computed enthalpies of binding using a larger basis set for Mo(PMe3)(2)(CO)(3)L show a better fit to experimental data than that for Mo((PPr3)-Pr-i)(2)(CO)(3)L using a smaller basis set. Crystal structures of Mo((PPr3)-Pr-i)(2)(CO)(3)(AdCN), W((PPr3)-Pr-i)(2)(CO)(3)(Me2NCN), W ((PPr3)-Pr-i)(2)(CO)(3)(2,6-F2C6H3CN), W((PPr3)-Pr-i)(2)(CO)(3)(2,4,6-Me3C6H2CN), W((PPr3)-Pr-i)(2)(CO)(3)(2,6-Me(2)pz), W((PPr3)-Pr-i)(2)(CO)(3)(AdCN), Mo((PPr3)-Pr-i)(2)(CO)(3)(AdNC), and W((PPr3)-Pr-i)(2)(CO)(3)(AdNC) are reported.

  DOI：

  10.1021/ic900764e
• 作为产物：
  描述：

  mer,trans-tricarbonylbis(triisopropylphosphite)(η1-sulfur dioxide)molybdenum 在 吡啶 作用下， 以 吡啶 为溶剂， 生成 Mo(py)(CO)3(P(i)Pr3)2
  参考文献：
  名称：

  Schwefel（IV）-Verbindungen Als配体：III。结构和结合能力

  摘要：

  的类型的富电子二氧化硫络合物合成FAC -M（CO）3（DMPE）（η - 2 -SO 2），聚体-M（CO）3（DMPE）η 1 -SO 2），聚体，反式-M（CO）3（PR 3）2（η 1 -SO 2）（M =铬，钼，W; PR 3 = PPH 2我，P（OME）3，P（OI-PR）3），反式-Mo（CO）2（DPPE） - （PR 3）（η 1 -SO 2）（PR3 = PME 3，PPH 2我，裨-PR 3），以及FAC -Cr（CO）3（联吡啶）（η 2 -SO 2），和FAC -Mo（CO）3（乙腈）2（η描述了2- SO 2。这些化合物的结构是基于NMR和振动光谱法得出的。结果允许其向η的稳定性的各种因素的分析1和η 2种在接合模式{MSO 2 } 6层的复合物。在三羰基系列中SO 2 在某些情况下会伴随金属周围的立体化学变化而在反应中被吡啶取代。

  DOI：

  10.1016/s0022-328x(00)99203-9

文献信息

• Synthesis, Structure, and Thermochemistry of the Formation of the Metal−Metal Bonded Dimers [Mo(μ-TeAr)(CO)₃(PⁱP₃)]₂ (Ar = Phenyl, Naphthyl) by Phosphine Elimination from ^•Mo(TePh)(CO)₃(PⁱPr₃)₂
  作者：John J. Weir、James E. McDonough、George Fortman、Derek Isrow、Carl D. Hoff、Brian Scott、Gregory J. Kubas

  DOI：10.1021/ic061654x

  日期：2007.2.1

  The complexes ((TeAr)-Te-center dot)Mo(CO)(3)((PPr3)-Pr-i)(2) (Ar = phenyl, naphthyl; Pr-i = isopropyl) slowly eliminate (PPr3)-Pr-i at room temperature in a toluene solution to quantitatively form the dinuclear complexes [Mo(mu-TeAr)(CO)(3)((PPr3)-Pr-i)](2). The crystal structure of [Mo(mu-Te-naphthyl)(CO)(3)((PPr3)-Pr-i)](2) is reported and has a Mo-Mo distance of 3.2130 angstrom. The enthalpy of dimerization has been measured and is used to estimate a Mo-Mo bond strength on the order of 30 kcal mol(-1). Kinetic studies show the rate of formation of the dimeric chalcogen bridged complex is best fit by a rate law first order in ((TeAr)-Te-center dot)Mo(CO)(3)(P(i)Pr3)(2) and inhibited by added (PPr3)-Pr-i. The reaction is proposed to occur by initial dissociation of a phosphine ligand and not by radical recombination of 2 mol of ((TeAr)-Te-center dot)Mo(CO)(3)((PPr3)-Pr-i)(2). Reaction of ((TePh)-Te-center dot)Mo(CO)(3)((PPr3)-Pr-i)(2), with L = pyridine (py) or CO, is rapid and quantitative at room temperature to form PhTeTePh and Mo(L)(CO)(3)((PPr3)-Pr-i)(2), in keeping with thermochemical predictions. The rate of reaction of ((TeAr)-Te-center dot)W(CO)(3)((PPr3)-Pr-i)(2) and CO is first-order in the metal complex and is proposed to proceed by the associative formation of the 19 e(-) radical complex ((TePh)-Te-center dot)W(CO)(4)((PPr3)-Pr-i)(2) which extrudes a (TePh)-Te-center dot radical.