[W(NCH2Ph)(κ4-meso-o-C6H4(PPhCH2CH2PPh2)2)] | 1383788-61-1

• 英文名称: [W(NCH2Ph)(κ4-meso-o-C6H4(PPhCH2CH2PPh2)2)]
• CAS: 1383788-61-1
• 化学式: C₅₃H₄₉NP₄W
• 分子量: 1007.72
• InChiKey: JTPJUEJLLUVYNY-HUBVTLOYSA-N

反应信息

• 作为产物：
  描述：

  [WH4(κ4-meso-o-C6H4(PPhCH2CH2PPh2)2)] 、 苯甲腈 以 甲苯 为溶剂， 生成 [W(NCH2Ph)(κ4-meso-o-C6H4(PPhCH2CH2PPh2)2)] 、 [W(NCH2Ph)(κ4-meso-o-C6H4(PPhCH2CH2PPh2)2)]
  参考文献：
  名称：

  Tungsten(II) Alkylimido Complexes from Insertion of Nitriles into Tungsten Hydride: Alkylideneamido Intermediate Stage and Nitrene Group Transfer to Isocyanide

  摘要：

  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.

  DOI：

  10.1021/om3004338