{WH4(dppe)2} | 36352-27-9

• 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: {WH4(dppe)2}
• 英文别名: [WH₄(Ph₂PCH₂CH₂PPh₂)₂]；W(tetrahydride)(bis-(1,2-diphenyl-phosphino)ethane-κ²P)2；[WH₄(dppe)₂]；2-diphenylphosphanylethyl(diphenyl)phosphane;tungsten tetrahydride
• CAS: 36352-27-9
• 化学式: C₅₂H₅₂P₄W
• 分子量: 984.73
• InChiKey: NZOXFOVNXUQMOX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.43
• 重原子数：
  57.0
• 可旋转键数：
  8.0
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  {WH4(dppe)2} 在 氮 作用下， 以 环己烷 为溶剂， 以29%的产率得到trans-bis[1,2-bis(diphenylphosphino)ethane]bis(dinitrogen)tungsten(0)
  参考文献：
  名称：

  Photochemical reaction of phosphine hydride complexes of molybdenum and tungsten with molecular nitrogen

  摘要：

  DOI：

  10.1007/bf00950268
• 作为产物：
  描述：

  trans-bis[1,2-bis(diphenylphosphino)ethane]bis(dinitrogen)tungsten(0) 在 氢气 作用下， 以 苯 为溶剂， 生成 {WH4(dppe)2}
  参考文献：
  名称：

  四氢双（双（1,2-二苯基膦）乙烷）钼和钨的光物理和光化学行为：烯烃的光发射和光还原

  摘要：

  配合物 H/sub 4/M(DPPE)/sub 2/ 和 D/sub 4/M(DPPE)/sub 2/ (M = Mo, W; DPPE = 双 (1,2-二苯基膦)乙烷) 表现出发射在 2-甲基四氢呋喃中以 77/sup 0/K 光激发可见光。W 物质在 77/sup 0/K 时的发射寿命（约 13 μs）比 Mo 物质（约 90 μs）短，并且与物质是否/sup 1/H 或 /sup 2/H。W 物种的较短寿命表明 HN/sub 2/ 反键发射三重态，因为 298/sup 0/K 下的溶液光化学主要由 H/sub 2/ 损失决定。而 /sup 1/H 物种的寿命 (0.21)。数据表明，/sup 2/H 减少了从直接吸收达到的单重激发态的非辐射衰减。这种减少的非辐射衰变，通过系统间交叉以更高的效率产生发射三重态。在烯烃（例如，1-戊烯、顺式-2-戊烯、3,3-二甲基-1-戊烯、环戊烯）存在下照射

  DOI：

  10.1021/ja00390a023

文献信息

• The reactions of trans-[MoH4(Ph2PCH2CH2PPh2)2] with RCO2CCH (R = Me or Et) in the presence of acids. Preparation of hydrido-σ-alkenyl complexes of molybdenum(IV)
  作者：Neimat Kashef、Raymond L. Richards

  DOI：10.1016/0022-328x(89)87029-9

  日期：1989.4

  Reaction of trans-[MoH4(dppe)2] (dppe = Ph2PCH2CH2PPh2) with RCO2CCH (R = Me or Et) in the presence of HBF4 in tetrahydrofuran (thf) gives the carboxylato-σ-alkenyl complexes [MoH2CHCHC(O)OR}(dppe)2]BF4, whereas if HBr is used as acid, decarboxylation of the alkenyl ligand occurs to give the complexes [MoBrH2(CHCHR)(dppe)2].

  的反应的反式- [卫生部4（DPPE）2 ]（DPPE =苯基2 PCH 2 CH 2 PPH 2）与RCO 2 CCH（R = Me或Et）在HBF的存在下4在四氢呋喃（THF），得到羧基-σ-烯基配合物[MoH2 CHCHC（O）OR}（DPPE）2 ] BF 4，而如果使用HBr作为酸，则烯基配体发生脱羧反应，得到配合物[MoBrH 2（CHCHR ）（DPPE）2 ]。
• EPR detection and characterisation of a paramagnetic Mo(<scp>iii</scp>) dihydride intermediate involved in electrocatalytic hydrogen evolution
  作者：Christopher Prior、Lee R. Webster、Saad K. Ibrahim、Joseph A. Wright、Ali F. Alghamdi、Vasily S. Oganesyan、Christopher J. Pickett

  DOI：10.1039/c5dt04432d

  日期：——

  EPR spectroscopy and theoretical data show that the slow heterogeneous electron-transfer kinetics associated with the reduction of an 18-electron Mo(iv) acetato dihydride are a consequence of an η²–η¹ rearrangement of the carboxylate ligand which gives a unique paramagnetic 17-electron Mo(iii) dihydride.

  EPR光谱和理论数据表明，与还原18电子Mo（IV）乙酸二氢化物相关的缓慢异质电子转移动力学是由羧酸配体的η2-η1重排引起的，这产生了一种独特的顺磁性17电子Mo（III）二氢化物。
• Kinetics and mechanism of the transfer hydrogenation and double bond migration of 1-hexene catalyzed by molybdenum complexes
  作者：Takashi Tatsumi、Makoto Shibagaki、Hiroo Tominaga

  DOI：10.1016/0304-5102(84)85036-1

  日期：1984.4

  transfer hydrogenation and double bond migration of 1-hexene catalyzed by trans-Mo(N2)2(dpe)2 (dpe = Ph2PCH2CH2PPh2) has been studied. The stoichiometric reaction of 1-hexene with MoH4(dpe)2 suggests that the active species for the hydrogenation is MoH2(dpe)2 and that for the double bond migration it is Mo(dpe)2. The double bond migration is suppressed in the hydrogenation of 1-hexene by molecular hydrogen

  研究了反式-Mo（N 2）2（dpe）2（dpe = Ph 2 PCH 2 CH 2 PPh 2）催化的1-己烯转移加氢和双键迁移的机理。1-己烯与MoH4（dpe）2的化学计量反应表明，氢化的活性物质为MoH 2（dpe）2，而双键迁移的活性物质为Mo（dpe）2。在1-己烯被分子氢加氢时，双键迁移受到抑制，形成了适量的己烷。Mo（C 2 H 4）2（dpe）2与2-丙醇的反应表明，双重途径可用于转移加氢。但是，氢从2-丙醇转移到1-己烯的动力学表明，主要途径涉及催化剂与2-丙醇的反应，生成氢化物，然后是1-己烯配位。通过2-烷基机理推断在2-丙醇存在下发生的双键迁移与在没有2-丙醇存在下的机理不同。
• Synthesis and Reactivities of Pyrrolylimido Complexes of Molybdenum and Tungsten: Formation of Pyrrole and N-Aminopyrrole from Molecular Nitrogen
  作者：Hidetake Seino、Youichi Ishii、Takao Sasagawa、Masanobu Hidai

  DOI：10.1021/ja00154a019

  日期：1995.12

  Hydrazido(2-) complexes trans-[MX(NNH2)(dppe)(2)](+) (M = Mo, W; X = F, Cl; dppe = Ph(2)PCH(2)CH(2)PPh(2)) and cis,mer-[WX(2)(NNH2)(PMe(2)Ph)(3)] (X = Cl, Br), which are readily derived from trans-[M(N-2)(2)(dppe)(2)] (1) and cis-[W(N-2)(2)(PMe(2)Ph)(4)] by protonation, condensed with 2,5-dimethoxytetrahydrofuran to afford pyrrolylimido complexes of the type trans-[MX(NNCH=CHCH=CH)(dppe)(2)](+) (3(+)) and cis,mer-[WX(2)(NNCH=CHCH=CH)(PMe(2)Ph)(3)] (6), respectively. Their structures were characterized spectroscopically and further confirmed by X-ray diffraction study. Electrophilic substitution reactions at the pyrrole ring in complexes 3(+) occurred selectively at the beta-position to give the corresponding beta-substituted pyrrolylimido complexes trans- [MX(NNCH=C(E)CH=CH)(dppe)(2)](+) (E Br, CN, SO3-, COR), although only chlorination of 3(+) with N-chlorosuccinimide in THF took place predominantly at the a-position. This beta-regioselectivity is in sharp contrast to the a-regioselectivity of free pyrrole and is probably caused by the steric effect of the dppe ligands. Complexes 3(+) were readily reduced under ambient conditions with LiAlH4 to liberate pyrrole and N-aminopyrrole in high yields. Further, the tetrahydrido complexes [MH(4)(dppe)(2)], which can be converted back into the original dinitrogen complexes 1, were recovered in moderate yields after the reduction. This accomplishes the synthetic cycle for pyrrole and N-aminopyrrole starting from the dinitrogen complexes 1. beta-Heptylpyrrole was also prepared by starting from 3c(+) (M = W, X = Cl) by the beta-selective heptanoylation followed by the reduction with LiAlH4. On the other hand, reduction of 6b (X = Br) with LiAlH4 predominantly produced pyrrole, whereas treatment of 6b with KOH/EtOH liberated N-aminopyrrole in a high yield.
• Photochemical interaction of phosphine hydride complexes of molybdenum and tungsten with carbon monoxide
  作者：A. P. Pivovarov、Yu. V. Gak、L. M. Ioffe、A. P. Borisov、V. D. Makhaev

  DOI：10.1007/bf00953149

  日期：1983.6