W(CN(2,6-Me2C6H3))2(κ4-meso-o-C6H4(PPhC2H4PPh2)2) | 1266740-37-7

• 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: W(CN(2,6-Me2C6H3))2(κ4-meso-o-C6H4(PPhC2H4PPh2)2)
• CAS: 1266740-37-7
• 化学式: C₆₄H₆₀N₂P₄W
• 分子量: 1164.94
• InChiKey: GCZOJFCWWMJLDD-HUBVTLOYSA-N

反应信息

• 作为产物：
  描述：

  WH4(κ4-meso-o-C6H4(PPhC2H4PPh2)2)*0.5C6H5CH3 、 2,6-二甲基苯基异腈 以 甲苯 为溶剂， 以64%的产率得到W(CN(2,6-Me2C6H3))2(κ4-meso-o-C6H4(PPhC2H4PPh2)2)
  参考文献：
  名称：

  含四膦配体meso-o-C6H4(PPhCH2CH2PPh2)2的钼和氢化钨配合物的制备和反应

  摘要：

  [Mo(κ 2 -dppe)(κ 4 -P4)] (1a) {dppe = PPh 2C H 2 CH 2 PPh 2 , P4 = meso-oC 6 H 4 (PPhCH 2 CH 2 PPh 2 ) 2 的反应} 在室温下用 1 个大气压的 H 2 选择性地得到 [MoH 2 (κ 2 -dppe)(κ 3 -P4)] (3a)。1a 的 W 类似物与 1 个大气压的 H 2 在 80 °C 反应形成 [WH 2 (κ 2 -dppe)-(κ 3 -P4)] 和 [WH 4 (κ 4 -P4)] 的混合物 ( 5b)，后者可以通过在 50°C 下在乙醇中用 NaBH 4 还原 [WBr 2 (κ 4 -P4)] 来干净地制备。配合物5b的分子结构与相关配合物[WH 4 -(dppe) 2 ]的分子结构不同，显示出更高的反应性。WH 键的插入发生在 5b 与 CS 2 在 50°C 的反应中，得到亚甲基二硫醇复合物

  DOI：

  10.1002/ejic.201000855

文献信息

• Tungsten(II) Alkylimido Complexes from Insertion of Nitriles into Tungsten Hydride: Alkylideneamido Intermediate Stage and Nitrene Group Transfer to Isocyanide
  作者：Qi Xiu Dai、Hidetake Seino、Yasushi Mizobe

  DOI：10.1021/om3004338

  日期：2012.7.23

  The tetrahydrido complex [WH4(kappa(4)-P4)] (P4 = meso-o-C6H4(PPhCH2CH2PPh2)(2)) reacted with aliphatic nitriles AkCN at 80 degrees C in toluene to afford a series of the imido complexes, [W(NCH(2)Ak)(kappa(4)-P4)] (2). Similar reactions with aromatic nitriles ArCN proceeded stepwise, leading to formation of the hydrido-alkylideneamido complexes [WH(N=CHAr)(kappa(4)-P4)] (3) at the first stage and a subsequent isomerization into the imido complexes [W(NCH2Ar)(kappa(4)-P4)] (4). Conversion of 3 into 4 was accelerated by electron-rich Ar groups such as p-CH3OC6H4, while it was completely inhibited when Ar was the considerably electron-deficient p-CF3C6H4. An X-ray crystallographic study on 2 (Ak = p-ClC6H4CH2) and 4 (Ar = p-tolyl) has disclosed a distorted-square-pyramidal coordination geometry, in which the apical position is occupied by the imido ligand with a W-II-N triple bond. An almost linear W-II=N=C linkage of 3 (Ar = p-tolyl) has also been determined. Complex 2 was capable of nitrene group transfer to isocyanide to produce carbodiimide.