trans,mer-bis(triisopropylphosphine)(N-methylpyrazinium)tricarbonylmolybdenum(0) hexafluorophosphate | 177035-11-9

• 英文名称: trans,mer-bis(triisopropylphosphine)(N-methylpyrazinium)tricarbonylmolybdenum(0) hexafluorophosphate
• 英文别名: [Mo(P(i)Pr3)2(CO)3(4-methylpyrazine)][PF6]；[Mo(P(i)Pr3)2(CO)3(4-Mepz)][PF6]
• CAS: 177035-11-9
• 化学式: C₂₆H₄₉MoN₂O₃P₂*F₆P
• 分子量: 740.538
• InChiKey: ZQAKRVXJECFERO-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：

  trans,mer-bis(triisopropylphosphine)(N-methylpyrazinium)tricarbonylmolybdenum(0) hexafluorophosphate 、 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：

  Mo(CO)3(P(i)Pr3)2 、 N-methyl-pyrazinium hexafluorophosphate 以 甲苯 为溶剂， 以90%的产率得到trans,mer-bis(triisopropylphosphine)(N-methylpyrazinium)tricarbonylmolybdenum(0) hexafluorophosphate
  参考文献：
  名称：

  UV-vis, IR and EPR spectroelectrochemical study of the EC redox transition [(PR3)n(CO)3(R′-pz)M]+/0; M = Mo, W; R′-pz = N-alkylpyrazinium; R = isopropyl, cyclohexyl; n = 1 or 2

  摘要：

  The title complexes, isolated as trans,mer-configurated salts [(PR(3))(2)(CO)(3)(R'-pz)M](PF6), display a strong pi interaction between the zerovalent metal center and the excellent pi acceptor ligands R-pz(+). The solvatochromism of the long-wavelength metal-to-ligand charge transfer (MLCT) absorption as analyzed in particular for [(PCy(3))(2)(CO)(3)(CH3(CH2)(17)-pz)W](PF6) correlates not with established MLCT parameters but with the donor numbers of the solvents. The seemingly reversible one-electron oxidation and reduction processes were studied by spectroelectrochemical techniques with regard to EPR, carbonyl vibrational and UV-vis/NIR spectroscopic features. Whereas oxidation leads to labile M(I) species with 17 valence electrons, the reduction is centered at the R'-pz(+) ligand and causes a rapid reversible dissociation of one PR(3) group from the metal (EC(rev) process). Both EPR and IR data suggest pentacoordination at the 16 + delta valence electron centers in the neutral species [(PR(3)(CO)(3)(R'-pz)M](.).

  DOI：

  10.1016/0022-328x(95)05933-g