[WH4(κ4-meso-o-C6H4(PPhCH2CH2PPh2)2)] | 1266740-34-4

• 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(κ4-meso-o-C6H4(PPhCH2CH2PPh2)2)]
• CAS: 1266740-34-4
• 化学式: C₄₆H₄₆P₄W
• 分子量: 906.616
• InChiKey: QXUAALLUODGCKA-QKGNLNRWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.74
• 重原子数：
  51.0
• 可旋转键数：
  6.0
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.09
• 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：

  正辛腈 、 [WH4(κ4-meso-o-C6H4(PPhCH2CH2PPh2)2)] 以 甲苯 为溶剂， 生成 [W(NCH2(n-C7H15))(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

文献信息

• Transformations of aryl isothiocyanates on tetraphosphine tungsten complexes and reactivity of the resulting dithiocarbonimidate ligand
  作者：Qi Xiu Dai、Hidetake Seino、Yasushi Mizobe

  DOI：10.1039/c1dt11201e

  日期：——

  Treatment of [WH4(κ4-P4)] (3: P4 = meso-o-C6H4(PPhCH2CH2PPh2)2) with aryl isothiocyanate ArNCS at 50 °C afforded the dithiocarbonimidate-isocyanide complex [W(κ2-S2CNAr)(CNAr)(κ4-P4)] (4) in moderate yields. The reaction also produced ArNHCH3 and a small amount of ArNH2. The yield of the hydrodesulfurization product ArNHCH3 increased when the reaction was conducted under H2 (up to 0.65 equiv. to 3 for Ar = p-MeC6H4 (Tol)). Complex 4 was proposed to be formed via reductive disproportionation of two ArNCS molecules on a zero-valent W species generated by dissociation of H2 from 3. The reaction of W(0) complex [W(dppe)(κ4-P4)] (dppe = Ph2PCH2CH2PPh2) with ArNCS also yielded 4 accompanied by free dppe, in contrast to that of [Mo(dppe)(κ4-P4)], which had been previously reported to undergo sulfur-atom transfer to phosphine ligands. The dithiocarbonimidate ligands in 4a (Ar = Tol) received the addition of electrophiles [PhMe2NH][BF4], MeI, and PhCOCl selectively at the N atom to afford the cationic dithiocarbamate complexes [W(κ2-S2CNHTol)(CNTol)(κ4-P4)][BF4] (6), [Wκ2-S2CN(Me)Tol}(CNTol)(κ4-P4)]I (7), and [Wκ2-S2CN(COPh)Tol}(CNTol)(κ4-P4)]Cl (8). Complexes 4a, 6, 7, and 8 have been characterized by spectroscopic and crystallographic methods, and the donor strengths of their κ2-dithio ligands are discussed.

  50 °C 时，用芳基异硫氰酸酯 ArNCS 处理[WH4(κ4-P4)]（3：P4 = 介-C6H4(PPhCH2CH2PPh2)2），可得到二硫代碳亚氨基异氰酸酯复合物[W(κ2-S2CNAr)(CNAr)(κ4-P4)]（4），产率中等。反应还产生了 ArNHCH3 和少量 ArNH2。在 H2 条件下进行反应时，加氢脱硫产物 ArNHCH3 的产率增加（Ar = p-Me (Tol) 时，产率高达 0.65 等价于 3）。根据推测，络合物 4 是通过两个 ArNCS 分子与 3 中解离出的 H2 生成的零价 W 物种发生还原歧化反应而形成的。W(0) 复合物 [W(dppe)(κ4-P4)]（dppe = Ph2PCH2CH2PPh2）与 ArNCS 反应也生成了伴有游离 dppe 的 4，这与之前报道的[Mo(dppe)(κ4-P4)]相反，后者发生了硫原子向膦配体的转移。4a 中的二硫代羰亚胺配体（Ar = Tol）在亲电体 [PhMe2NH][BF4]、MeI、和 PhCOCl，从而得到阳离子二硫代氨基甲酸酯配合物 [W(κ2-S2CNHTol)(CNTol)(κ4-P4)][BF4] (6)、[Wκ2-S2CN(Me)Tol}(CNTol)(κ4-P4)]I (7) 和 [Wκ2-S2CN(COPh)Tol}(CNTol)(κ4-P4)]Cl (8)。配合物 4a、6、7 和 8 已通过光谱和晶体学方法进行了表征，并讨论了它们的 κ2-二硫配体的供体强度。