bis{1,2-bis(dimethylphosphino)ethane}diiodovanadium(II) | 148753-28-0

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: bis{1,2-bis(dimethylphosphino)ethane}diiodovanadium(II)
• CAS: 148753-28-0
• 化学式: C₁₂H₃₂I₂P₄V
• 分子量: 605.032
• InChiKey: QTJKWIWVNHSRSY-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  6.71
• 重原子数：
  19.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  V(1,2-bis(dimethylphosphino)ethane)2(CF3SO3)2 、 lithium iodide 以 乙醚 、 二氯甲烷 为溶剂， 以35%的产率得到bis{1,2-bis(dimethylphosphino)ethane}diiodovanadium(II)
  参考文献：
  名称：

  Vanadium(II) Salts in Pyridine and Acetonitrile Solvents

  摘要：

  Earlier work on the interaction of V(II ) salts with pyridine and acetonitrile as solvents has been extended. The structure of the compound VPy(4)(O3SCF3)(2), 1, an intermediate in many of the preparations, has been determined by X-ray diffraction. Analogous solids with I-, Br-, Cl-, SCN-, N-3(-), PhS(-), EtS(-), and BH4- as counterions have been prepared. Attempts to prepare solids with PhO(-), HO-, MeO(-), Ph(-), CN-, AlH4-, and H- failed, but the tetrapyridine complexes were prepared by titrating a solution of 1 in pyridine with the lithium salt of each anion (in the case of H-, the anion was Et(3)BH(-)) to an end point observed at the 1:2 ratio. Comparisons in a number of cases of the absorption spectra and of the cyclovoltammetric behavior of the tetrapyridine salts in pyridine and in CH2Cl2 show the species in the two solvents to be the same and to correspond to the composition of the solids. Intercomparisons of the absorption spectra in pyridine suggest that the complexes with the aforementioned anions all have similar structures: four pyridine molecules situated equatorially-on the basis of crystal structure determinations, in a propeller arrangement--and the anions occupying axial positions. The initial absorption spectrum of a solution of VPy(4)(PF6)(2) in pyridine changes to that shown by a solution of VPy(6)(PF6)(2) or of VPy(6)(BPh(4))(2), and we conclude that with these weakly nucleophilic anions VPy(6)(2+) is the dominant form of V(II) in pyridine solution. In every case, the prominent feature of the absorption spectrum is a band envelope consisting of a maximum that ranges from 586 to 400 nm accompanied by a shoulder which usually lies on ther low-energy side of the dominant peak and which in these cases we assign to nu(CT) and nu(1)'', respectively. The latter is the higher energy component of the two transitions nu(1)' and nu(1)'', which arise from nu(1) (octahedral) when the symmetry is reduced to axial. Energy correlations suggest that nu(CT) always lies at higher energy than nu(1)'', so that when the shoulder lies on the high-energy side of the dominant peak, epsilon(nu(1)'') exceeds epsilon(nu(CT)) In a number of cases nu(1)' is observed. It is of much lower intensity than nu(1)'', and the wavelengths of the transitions lie in the range of 600 nm and higher and vary with the nature of ligands as observed in other cases of axial symmetry. The absorption characteristics of Vqy(6)(2+) resemble those of the tetrapyridine complexes, suggesting that the propellerlike arrangement is retained in this species, two pyridines replacing the anions in the axial positions; i.e., the axial and equatorial pyridines are inequivalent.

  DOI：

  10.1021/ic00127a013

文献信息

• Synthesis and structural studies of complexes of vanadium(II) and vanadium(III) halides with tertiary phosphines
  作者：David G.L. Holt、Leslie F. Larkworthy、David C. Povey、Gallienus W. Smith、G.Jeffery Leigh

  DOI：10.1016/s0020-1693(00)91450-6

  日期：1993.5

  (XCl or Br; dppe=1,2- bis(diphenylphosphino)ethane) could not be isolated from methanol, but were obtained from tetrahydrofuran (thf). All are typical vanadium(II) complexes, and [VCl2(depe)2] and [VCl2(dppe)2]·2thf have trans structures. The VCl bond distances, 2.445(2) and 2.420(1) A, respectively, are similar to that in the known complex [VCl2(dmpe)2], but the VP bond distances are longer by approximately

  摘要由金属和适当的酸制备的卤化钒（II）[VCl2（H2O）4]和[V（ ）6] Br2与1,2-双（二甲基膦基）乙烷（dmpe）和1，在甲醇中的2-双（二乙基膦基）乙烷（去），得到[VX2（dmpe）2]和[VX2（depe）2]（X ＝ Cl或Br）。碘配合物是从[V（MeOH）6] I 2获得的，尽管[VI 2（depe）2]不是纯净的。不能从甲醇中分离出配合物[VX2（dppe）2]·2thf（X ＝ Cl或Br； dppe ＝ 1，2-双（二苯基膦基）乙烷），而是从四氢呋喃（thf）获得的。它们都是典型的钒（II）络合物，[VCl2（depe）2]和[VCl2（dppe）2]·2thf具有反式结构。VCl的键距分别为2.445（2）和2.420（1）A，与已知络合物[VCl2（dmpe）2]中的相似，但VP的键距更长，约为0.06 A和PVP角小c。3°，可能是由于赤