W(PhC.tplbond.CPh)3(NCMe) | 138899-91-9

• 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: W(PhC.tplbond.CPh)3(NCMe)
• 英文别名: W(NCMe)(η2-PhC2Ph)3；W(NCMe)(η-PhCCPh)3；W(NCMe)(η2-C2Ph2)3；Acetonitrile;2-phenylethynylbenzene;tungsten
• CAS: 138899-91-9
• 化学式: C₄₄H₃₃NW
• 分子量: 759.603
• InChiKey: YSLDOWXGTIASFN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.79
• 重原子数：
  46
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.02
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  W(PhC.tplbond.CPh)3(NCMe) 、 二苯基甲氧基膦 以 苯 为溶剂， 以91%的产率得到W(PhC.tplbond.CPh)3(PPh2Me)
  参考文献：
  名称：

  Phosphine complexes of tungsten(0) poly(alkyne); crystal structures of W(PhCCPh)3(PMe3) and W(TolCCTol)2(η4-C4Tol4)(PMe3)

  摘要：

  Reactions of W(PhC=CPh)(3)L (L=CO or NCMe) with PMe3, PPh2Me and PPh3 produce W(PhC=CPh)(3)(PMe3), W(PhC=CPh)3(PPh2Me) and W(PhC=CPh)(3)(PPh3), respectively. Reaction of W(PhC=CPh)(3)(NCMe) with 1,1'-bis(diphenylphosphino) ferrocene (dppf) forms W(PhC=CPh)(3)(eta(1)-dppf) and [W(PhC=CPh)(3)](2)(eta(1),eta(1)-dppf). Treating W(RC=CR)(2)(eta(4)-C4R4) (NCMe) (R=Ph and Tol) with PMe3 affords W(RC=CR)(2)(eta(4)-C4R4)(PMe3). W(PhC=CPh)(3)(PMe3) crystallizes in the space group P (3) over bar with a=14.000(4), c=11.183(3) Angstrom, V=1898.3(7) Angstrom(3), Z=2 and R-F=0.032. W(TolC=CTol)(2)(eta(4)-C(4)Tol(4))(PMe3) crystallizes in the space group P2(1)/c with a=13.588(2), b=19.289(5), c=22.150(5) Angstrom, beta=90.57(2)degrees, V=5805.(2) Angstrom(3), Z=4 and R-F= 0.055.

  DOI：

  10.1016/s0020-1693(96)05385-6
• 作为产物：
  描述：

  tris(diphenylacetylene)tungsten monocarbonyl 、 乙腈 在 十二/十四烷基二甲基氧化胺 作用下， 以 乙腈 为溶剂， 以80%的产率得到W(PhC.tplbond.CPh)3(NCMe)
  参考文献：
  名称：

  Syntheses of W(PhCCPh)3(η1-PPh2CH2PPh2) and W(PhCCPh)3(PPh3) from W(PhCCPh)3(NCCH3)

  摘要：

  DOI：

  10.1016/0022-328x(92)83089-z

文献信息

• Alkyne−Alkyne Coupling Reactions with W(CO)(PhC⋮CPh)₃ and W(NCMe)(PhC⋮CPh)₃
  作者：Wen-Yann Yeh、Chi-Lin Ho、Michael Y. Chiang、I-Ting Chen

  DOI：10.1021/om9702340

  日期：1997.6.1

  mainly the metallacyclic complex W(PhC⋮CPh)(η8-C8Ph8) (10). Compound 10 reacts with carbon monoxide to afford 3 and 4, while thermolysis of pure 10 results in 5 exclusively. The reaction mechanism has been explored by C-13 labeling experiments. The structures of 7 and 10 have been established by an X-ray diffraction study. The bonding of pentaphenylcyclopentadienyl ligands of 7 is best described as

  加热W（CO）（PHC⋮CPH）3（1）和二苯基乙炔在密封管通向炔炔偶联，得到W（CO）（PHC⋮CPH）2（η 4 -C 4博士4）（2） ，W（CO）（PHC⋮CPH）（η 5 -C 3博士3（C 5博士5））（3）和W（CO）（PHC⋮CPH）（η 6 -C 3博士3（C 5 Ph 5））（4）和钨茂金属低聚物[W（C 5 Ph 5）2 ]x（ 5）。氧化5通过二碘，得到W（η 5 -C 5博士5） 2（I） 2（ 6），它被转换成氧络合物W（η 5 -C 5博士5） 2（O）（ 7）由在湿的二氯甲烷溶液中用AgBF 4处理。W（NCMe）（PHC⋮CPH）的反应3（ 8二苯基乙炔）和1当量产生W（NCMe）（PHC⋮CPH） 2（η 4 -C 4博士4）（ 9），而在过量的二苯基乙炔的存在类似反应，得到主要是metallacyclic复杂W（光子晶体⋮CPH）（η 8 -C 8博士
• C₆₀-induced alkyne–alkyne coupling and alkyne scission reactions of a tungsten tris(diphenylacetylene) complex
  作者：Wen-Yann Yeh

  DOI：10.1039/c0cc04034g

  日期：——

  Reaction of W(NCMe)(eta(2)-PhC identical withCPh)(3) with C(60) affords W(eta(3)-NC(Me)C(60))(eta(4),eta(2)-C(6)Ph(6)) (2) and W( identical withCPh)(NCMe)(eta(2)-C(60)) (eta(3),eta(2)-C(5)Ph(5)) (3). The hexaphenylbenzene species of 2 shows an eta(4)-butadiene + eta(2)-olefin bonding mode and the nitrile carbon is inserted into one 6:5-ring junction of C(60). Compound 3 contains an eta(3),eta(2)-p

  W（NCMe）（eta（2）-PhC与CPh）（3）相同的反应与C（60）得到W（eta（3）-NC（Me）C（60））（eta（4），eta（2） ）-C（6）Ph（6））（2）和W（与CPh）（NCMe）（eta（2）-C（60））（eta（3），eta（2）-C（5）Ph （5））（3）。2的六苯基苯物种显示出eta（4）-丁二烯+ eta（2）-烯烃键合模式，并且腈碳插入到C（60）的一个6：5环结中。化合物3包含由二苯乙炔配体的2 + 2 + 1环化和断裂反应而来的η（3），η（2）-五苯基环戊二烯基和苄基炔基。
• W(O) (η3-PPh2(o-C6H4)C5Ph4H) (η2-C2Ph2): A complex containing oxo and metallacyclohexadiene ligands from CO bond activation and alkyne coupling reactions of W(NCMe) (η2-C2Ph2)3 with PPh2(o-C6H4)C(O)H
  作者：Jin-Wen Yang、Chi-Shian Chen、Huei-Fang Dai、Chia-Hsiang Chen、Wen-Yann Yeh

  DOI：10.1016/j.jorganchem.2011.01.025

  日期：2011.4

  Reaction of W(NCMe) (eta(2)-C2Ph2)(3) (1) and PPh2(o-C6H4)C(=O)H in refluxing toluene affords W(O) (eta(3)-PPh2(o-C6H4)C5Ph4H) (eta(2)-C2Ph2) (2). The structure of 2 reveals that an oxygen atom and a pentadienyl group are attached to the tungsten center, apparently arising from activation of the formyl C=O bond and coupling of the diphenylacetylene ligands. (C) 2011 Elsevier B.V. All rights reserved.
• WCl(η²-C₂Ph₂)(η⁶-C₆Ph₆H):  A Compound Containing a Metallacycloheptatriene Unit from Trimerization of Diphenylacetylene with W(NMe₃)(η²-C₂Ph₂)₃
  作者：Wen-Yann Yeh、Shie-Ming Peng、Gene-Hsiang Lee

  DOI：10.1021/om0201009

  日期：2002.7.1

  W(NCMe)(eta(2)-C2Ph2)(3) (1) has been previously synthesized by the reaction of W(CO)(eta(2)-C2Ph2)3 Wit Me3NO in acetonitrile, while the same treatment in THF leads to the trimethylamine complex W(NMe3)(eta(2)-C2Ph2)(3) (2). Compound 2 is reactive. Stirring a mixture of 2 and diphenylacetylene in dichloromethane at room temperature affords WCl(eta(2)-C2Ph2)(eta(6)-C6Ph6H) (3), which apparently arises from trimerization of the alkyne ligands concomitant with solvent activation. The structures of 1-3 have been determined by an X-ray diffraction study. A carbene W=C double bond is evidenced in 3.
• Reaction of [W(η²-PhC₂Ph)₃(NCMe)] with o-diphenylphosphino-styrene and -allylbenzene; evidence for novel carbon–carbon double and triple bond cleavage and alkyne insertion reactions
  作者：Gareth A. Cairns、Nicholas Carr、Michael Green、Mary F. Mahon

  DOI：10.1039/cc9960002431

  日期：——

  Reaction of [W(eta(2)-PhC(2)Ph)(3)(NCMe)] with o-diphenyl-phosphino-styrene or -allylbenzene leads to either novel reorganisation reactions involving cleavage of carbon-carbon double and triple bonds, or unusual insertion reactions by PhC(2)Ph into carbon-hydrogen bonds.