[W(IV)Cl4(1,2-bis(diphenylphosphio)ethane)] | 21712-53-8

• 英文名称: [W(IV)Cl4(1,2-bis(diphenylphosphio)ethane)]
• 英文别名: [WCl4(dppe)]；WCl4(dppe)
• CAS: 21712-53-8
• 化学式: C₂₆H₂₄Cl₄P₂W
• 分子量: 724.086
• InChiKey: VENKAIBDWZUMDB-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：
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• 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：

  [W(IV)Cl4(1,2-bis(diphenylphosphio)ethane)] 、 N-phenyl-N'-(trimethylsilyl)hydrazine 以 苯 为溶剂， 以50%的产率得到[1,2-bis(diphenylphosphino)ethane]trichloro(phenyldiazenido)tungsten(IV)
  参考文献：
  名称：

  Ali, Hapipah Mohd.; Leigh, Jeffery G., Journal of the Chemical Society, Dalton Transactions, 1986, p. 213 - 216

  摘要：

  DOI：

文献信息

• The preparation and oxidation, substitution, and protonation reactions of trans-bis(dinitrogen)tetrakis(methyldiphenylphosphine)tungsten
  作者：Joseph Chatt、Alan J. Pearman、Raymond L. Richards

  DOI：10.1039/dt9770002139

  日期：——

  The complex trans-[W(N2)2(PMePh2)4] has been prepared. It gives trans-[W(N2)2(PMePh2)4][FeCl4] with an excess of FeCl3 in ethanol, and [W(N2)2(PMePh2)3L](L = NC5H5, NC5H4Me-3, NC5H4Me-4, or NC5H4CO2H-4) on treatment with L in tetrahydrofuran (thf). With dppe (Ph2PCH2CH2PPh2) in thf, trans-[M(N2)2(PMePh2)4](M = Mo or W) give [M(N2)2(PMePh2)2(dppe)]. Treatment of [W(N2)2(PMePh2)4] with hydrogen chloride

  已经制备了复杂的反式-[W（N 2）2（PMePh 2）4 ]。用乙醇中过量的FeCl 3生成反式-[W（N 2）2（PMePh 2）4 ] [FeCl 4 ] ，和[W（N 2）2（PMePh 2）3 L]（L = NC 5 H 5，NC 5 H 4 Me-3，NC 5 H 4 Me-4或NC 5 H 4 CO 2H-4），然后在四氢呋喃中用L处理（thf）。dppe（Ph 2 PCH 2 CH 2 PPh 2）在thf中，反式-[M（N 2）2（PMePh 2）4 ]（M = Mo或W）得到[M（N 2）2（PMePh 2）2（dppe）]。的治疗[W（N 2）2（PMePh 2）4 ]用在二氯甲烷中的氯化氢给出二氮（1摩尔）和[WCL 3（NHNH 2）（PMePh 2）2 ]，其用H甲醇中的2 SO 4生成肼（0.28 mol）和氨（0.23 mol），但主要是氨（0.76 mol）和少量肼（0
• Mo– and W–N2 and –CO complexes with novel mixed P/N ligands: Structural properties and implications to synthetic nitrogen fixation
  作者：Gerald C. Stephan、Christian Näther、Chinnappan Sivasankar、Felix Tuczek

  DOI：10.1016/j.ica.2007.06.046

  日期：2008.3

  group and one or more N -(diphenylphosphinomethyl)amine functions have been prepared and employed for the synthesis of Mo(0) and W(0) carbonyl and dinitrogen complexes. For comparison coordination of the literature-known ligand N , N -bis(diphenylphosphinomethyl)-methylamine (PNP, 1 ) to such systems has been investigated as well. Two new ligands are N , N -bis(diphenylphosphinomethyl)-2-aminopyridine (pyNP

  摘要制备了四个具有吡啶或噻唑基团和一个或多个N-（二苯基膦基甲基）胺官能团的新配体，并将其用于合成Mo（0）和W（0）羰基及二氮配合物。为了比较文献已知的配体N，还研究了N-双（二苯基膦基甲基）-甲胺（PNP，1）与这种系统的配合。两个新的配体是N，N-双（二苯基膦甲基）-2-氨基吡啶（pyNP 2，2）和N，N′-双（二苯基膦甲基）-2，6-二氨基吡啶（PpyP，3）。在第三个新的配体N-二苯基膦基甲基-2-氨基噻唑（thiazNP，4）中，吡啶基被噻唑取代。最后，合成了五齿配体N，N，N'，N'-四（二苯基膦甲基）-2,6-二氨基吡啶（pyN 2 P 4，5）。配体2的配位，基于三种钼羰基配合物[Mo（CO）3（NCCH 3）（pyNP 2）]（6），[Mo（CO）4（PpyP）]（ 7）和[Mo（CO）4（thiazNP）]（8），均在结构上进行了表征。此外，采用配体1和2，两个二氮配合物分别为[W（N
• Synthesis and reactivity of molybdenum and tungsten bis(dinitrogen) complexes supported by diphosphine chelates containing pendant amines
  作者：Charles J. Weiss、Amy N. Groves、Michael T. Mock、William G. Dougherty、W. Scott Kassel、Monte L. Helm、Daniel L. DuBois、R. Morris Bullock

  DOI：10.1039/c2dt12224c

  日期：——

  Molybdenum and tungsten bis(dinitrogen) complexes of the formula M(N2)2(PNP)2 (M = Mo and W) and W(N2)2(dppe)(PNP), supported by diphosphine ligands containing a pendant amine of the formula (CH2PR2)2NR′ = PRNR′PR (R = Et, Ph; R′ = Me, Bn), have been prepared by Mg reduction of metal halides under an N2 atmosphere. The complexes have been characterized by NMR and IR spectroscopy, X-ray crystallography

  分子式为M（N 2）2（PNP）2（M = Mo和W）和W（N 2）2（dppe）（PNP）的钼和钨双（二氮）配合物，由含侧基胺的二膦配体负载式（CH 2 PR 2）2 NR'= P [R ñ R' P [R（R =的Et中，Ph; R'= Me中，Bn），对已根据一个N制备由镁还原的金属卤化物2大气层。该复合物已通过NMR和IR光谱，X射线晶体学和循环伏安法表征。目标Mo和W双（二氮）化合物与CO的反应性导致形成二羰基配合物。
• Protonation Studies of a Tungsten Dinitrogen Complex Supported by a Diphosphine Ligand Containing a Pendant Amine
  作者：Charles J. Weiss、Jonathan D. Egbert、Shentan Chen、Monte L. Helm、R. Morris Bullock、Michael T. Mock

  DOI：10.1021/om401127v

  日期：2014.5.12

  complex without the pendant amine in the ligand backbone, trans-[W(N2)2(dppe)(depp)] (depp = Et2P(CH2)3PEt2), was synthesized and treated with HOTf, selectively generating a hydrazido complex, [W(NNH2)(OTf)(dppe)(depp)][OTf]. Computational analysis probed the proton affinity of three sites of protonation in these complexes: the metal, pendant amine, and N2 ligand. Room-temperature reactions with 100 equiv

  的治疗反式- [W（N 2）2（DPPE）（P的Et Ñ我P的Et）]（DPPE =苯基2 PCH 2 CH 2 PPH 2，P的Et Ñ我P的Et =的Et 2 PCH 2 N（Me）的CH 2 PET 2）与3当量的四氟硼酸（HBF 4 ·的Et 2 O）在-78℃下产生的七坐标氢化钨反式- [W（N 2）2（H）（DPPE）（P的Et ñMe P Et）] [BF 4 ]。在更高的温度下，还观察到侧链胺的质子化，得到反式-[W（N 2）2（H）（DPPE）（P Et N Me（H）P Et）] [BF 4 ] 2，形成肼基络合物[W（NNH 2）（DPPE）（P Et N Me（H）P Et）] [BF 4 ] 2作为次要产品。使用三氟甲磺酸（HOTf）获得了相似的产物混合物。质子化产物对热敏感，在环境温度下不持久。酸加成羰基类似物顺式-[W（CO）2（DPPE）（P Et N Me
• Metal hydrides as intermediates in the reactions of coordinated unsaturated hydrocarbons: formation of propyne by protonation of trans- [WH(η3-C5H5) (Ph2PCH2CH2PPh2)2]
  作者：Richard A. Henderson、David L. Hughes、Colin J. Macdonald、Kay E. Oglieve

  DOI：10.1016/s0020-1693(96)05588-0

  日期：1997.6

  The reaction of anhydrous HCl with trans-[WH(eta(3)-C3H5) (dppe)(2)] (dppe = Ph2PCH2CH2PPh2) in tetrahydrofuran gives [WH2Cl2-(dppe)(2)] together with propene and propyne. Detailed product analyses and kinetic studies demonstrate that propene and propyne are formed by protonation of the allyl residue and the metal, respectively. The most favoured site of protonation is the allyl group to form [WH(eta(2)MeCHCH(2)) (dppe)(2)](+), which releases propene and subsequently forms [WH2Cl2(dppe)(2)]. This is the exclusive hydrocarbon-forming pathway at low concentrations of HCl. The propyne-forming pathway dominates at high concentrations of acid, and involves diprotonation of the metal followed by loss of dihydrogen probably to give the coordinatively-unsaturated species, [WH(eta(3)-C3H5) (dppe)(2)](2+) which rearranges to [WH2(eta(2)-MeCCH) (dppe)(2)](2+), then releases propyne and subsequently forms [WH2Cl2(dppe)2]. The possible mechanisms for the allyl-to-propyne rearrangment are discussed in the light of GLC time-course experiments monitoring the release of the gases. The X-ray crystal structures of IMH(eta(3)-C3H5) (dppe)(2)] (M = Mo or W) show that both complexes have an approximate octahedral geometry about the metal with the hydride group trans to the allyl residue.