trans,mer-trichlorobis(dimethylphenylphosphine)(dimethylphenylphosphine oxide-κO)vanadium(III) | 136210-98-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: trans,mer-trichlorobis(dimethylphenylphosphine)(dimethylphenylphosphine oxide-κO)vanadium(III)
• CAS: 136210-98-5
• 化学式: C₂₄H₃₃Cl₃OP₃V
• 分子量: 587.747
• InChiKey: MUWXSRQJCDENTF-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  trans,mer-trichlorobis(dimethylphenylphosphine)(dimethylphenylphosphine oxide-κO)vanadium(III) 在 MgEtBr 、 dmpe 作用下， 生成 trans-VCl2(1,2-bis(dimethyl)phosphinoethane)2
  参考文献：
  名称：

  Studies on [VCl3(OPMe2Ph)(PMe2Ph)2]. Part 1. Synthesis, structure and reactivity of trans,mer-[VCl3(OPMe2Ph)(PMe2Ph)2], including the X-Ray crystal structure of mer-[VCl3(OPMe2Ph)(Et2PCH2CH2PEt2)]

  摘要：

  The complex trans,mer-[VCl3(OPMe2Ph)(PMe2Ph)2] has been prepared and its octahedral structure established by X-ray crystallography with V-Cl(av) 2.346(7), V-P 2.547(2), V-O 1.966(5) angstrom and VOP 157.4(4)-degrees. The phosphine ligands can be displaced by L-L = 2,2'-bipyridine, tetramethylethylene-diamine or Et2PCH2CH2PEt2 to give [VCl3(OPMe2Ph)(L-L)]. The X-ray crystal structure of mer-[VCl3(OPMe2Ph)(Et2PCH2CH2PEt2)] has been determined with V-Cl(av) 2.340(11), V-P 2.538(2) angstrom (trans to Cl), 2.501(2) angstrom (trans to O), V-O 2.049(4) angstrom and VOP 134.6(2)-degrees. Other reactions of trans,mer-[VCl3(OPMe2Ph)(PMe2Ph)2] have been investigated. Protonation with HCl gives [PHMe2Ph]-[VCl4(OPMe2Ph)], reaction with SiMe3(S2CNEt2) gives [V(S2CNEt2)3] and reduction with MgEtCl in the presence of an excess of Me2PCH2CH2PMe2 gives trans-[VCl2(Me2PCH2CH2PMe2)2].

  DOI：

  10.1039/dt9910001755
• 作为产物：
  描述：

  四氯化钒 、 二甲基苯基磷 以 正己烷 、 甲苯 为溶剂， 生成 trans,mer-trichlorobis(dimethylphenylphosphine)(dimethylphenylphosphine oxide-κO)vanadium(III)
  参考文献：
  名称：

  氯化钒的膦和氧化膦加合物：合成和结构研究

  摘要：

  摘要表征了VCl4与PEt3，PMe3，PMe2Ph，Et3PO和PhMe2PO的反应产物。化合物1 [HPEt3] [VCl4（PEt3）2]在空间群C2 / c中结晶，其中a = 17.422（2），b = 12.671（1），C = 13.390（1）A，β= 95.76（2） °，V = 2941（2）A3，Z = 4。[VCl4（PEt3）2]-阴离子的膦反式排列，平均VCl和VP距离分别为2.360（3）和2.551（4）A。化合物2，mer-VCl3（OPEt3）3在具有a = 13.310（4），b = 17.754（6），c = 12.383（3）A，V = 2926（2）A3和Z = 4；VCl距离（av。）= 2.396（7）和VO（av。）= 2.00（2）A.化合物3，mer-VCl3（PMe2Ph）2（OPMe2Ph）之前已在不同的空间报道过组，用正交晶系（Pmn21）晶胞结晶：a

  DOI：

  10.1016/0020-1693(93)03684-3

文献信息

• Synthesis, spectroscopic and EXAFS studies of vanadium complexes of trithioether ligands and crystal structures of [VCl3([9]aneS3)] and [VI2(thf )([9]aneS3)] ([9]aneS3 = 1,4,7-trithiacyclononane)
  作者：Sian C. Davies、Marcus C. Durrant、David L. Hughes、Christine Le Floc’h、Simon J. A. Pope、Gillian Reid、Raymond L. Richards、J. Roger Sanders

  DOI：10.1039/a802404i

  日期：——

  A series of vanadium-(II), -(III) and -(IV) macrocyclic thioether complexes has been synthesized and characterised by analytical, magnetic and spectroscopic methods. The new complexes reported are [V([9]aneS3)}2(µ-Cl)3]Cl ([9]aneS3 = 1,4,7-trithiacyclononane), [VI2(thf)([9]aneS3)], [VI2(ttob)] (ttob = 2,5,8-trithia[9]-o-benzenophane), [VX3([9]aneS3)] (X = Cl, Br or I), [VX3([10]aneS3)] ([10]aneS3 = 1,4,7-trithiacyclodecane), [VCl3(ttob)], [VCl3([16]aneS4)] ([16]aneS4 = 1,5,9,13-tetrathiacyclohexadecane), [(VX3)2(µ-[18]aneS6)] (X = Cl or Br, [18]aneS6 = 1,4,7,10,13,16-hexathiacyclooctadecane) and [VOCl2(ttob)]. The crystal structures of [VI2(thf)([9]aneS3)] and [VCl3([9]aneS3)] and EXAFS structural data for [VX3([9]aneS3)] and [VX3([10]aneS3)] are presented and discussed. The acyclic trithioether complexes [VX3MeC(CH2SMe)3}] (X = Cl or Br) and the complex [VI2(py)4] are also reported.

  合成了一系列钒-(II)、-(III)和-(IV)宏环硫醚配合物，并通过分析、磁性和光谱方法进行了表征。报道的新配合物包括 [V([9]aneS3)}2(µ-Cl)3]Cl ([9]aneS3 = 1,4,7-三硫环壬烷)、[VI2(thf)([9]aneS3)]、[VI2(ttob)]（ttob = 2,5,8-三硫[9]-o-苯环）、[VX3([9]aneS3)]（X = Cl、Br或I）、[VX3([10]aneS3)] ([10]aneS3 = 1,4,7-三硫环十烷)、[VCl3(ttob)]、[VCl3([16]aneS4)] ([16]aneS4 = 1,5,9,13-四硫环十六烷)、[(VX3)2(µ-[18]aneS6)]（X = Cl或Br，[18]aneS6 = 1,4,7,10,13,16-六硫环十八烷）和[VOCl2(ttob)]。提供并讨论了[VI2(thf)([9]aneS3)]和[VCl3([9]aneS3)]的晶体结构，以及[ 在VX3([9]aneS3)]和[VX3([10]aneS3)]的EXAFS结构数据。此外，还报道了非环状三硫醚配合物[ VX3MeC(CH2SMe)3}]（X = Cl或Br）和配合物[VI2(py)4]。
• Studies on [VCl₃(OPMe₂Ph)(PMe₂Ph)₂]. Part 2. Kinetic and mechanistic studies on the reaction of trans,mer-[VCl₃(OPMe₂Ph)(PMe₂Ph)₂] with 2,2′-bipyridine or Et₂PCH₂CH₂PEt₂at 25 °C
  作者：Richard A. Henderson

  DOI：10.1039/dt9910001761

  日期：——

  The kinetics of the reactions between trans,mer-[VCl3(OPMe2Ph)(PMe2Ph)2] and L-L = 2,2'-bipyridine or Et2PCH2CH2PEt2 to give mer-[VCl3(OPMe2Ph)(L-L)] have been studied in tetrahydrofuran (thf) at 25-degrees-C. Previous proposals that in solution the reactant is the solvento-species [VCl2(OPMe2Ph)(PMe2Ph)(thf)2]+ have been substantiated by kinetic studies which demonstrate that chloride must bind to the reactant prior to interaction with the substrates. The kinetics has been interpreted in terms of a series of associative-interchange steps. Strong evidence for the associative mechanism comes from the observation that the solvento-species does not react with L-L, a pattern which is inconsistent with a dissociative mechanism.