(η⁵-C₅Me₅)W(CO)₂{η³(Si,C,C)-Si(p-tolyl)₃} | 1419606-37-3

• 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: (η⁵-C₅Me₅)W(CO)₂{η³(Si,C,C)-Si(p-tolyl)₃}
• 英文别名: Cp*W(CO)₂{η³(Si,C,C)-Si(p-Tol)₃}；carbon monoxide;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;tris(4-methylphenyl)silanide;tungsten(2+)
• CAS: 1419606-37-3
• 化学式: C₃₃H₃₆O₂SiW
• 分子量: 676.583
• InChiKey: MZYLPTXRJIHXBC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.0
• 重原子数：
  37
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-羟基吡啶 、 (η⁵-C₅Me₅)W(CO)₂{η³(Si,C,C)-Si(p-tolyl)₃} 以 甲苯 为溶剂， 反应 0.17h， 以24%的产率得到Cp*W(CO)₂{κ²(Si,N)-Si(p-Tol)₂(OC₅H₄N)}
  参考文献：
  名称：

  Direct Conversion of a Si–C(aryl) Bond to Si–Heteroatom Bonds in the Reactions of η³-α-Silabenzyl Molybdenum and Tungsten Complexes with 2-Substituted Pyridines

  摘要：

  eta(3)-alpha-Silabenzyl complexes Cp*M(CO)(2)-{eta(3)(Si,C,C)-Si(p-Tol)(3)} (M = Mo (1-Mo), W (1-W)) reacted with 2-substituted pyridines NC5H4(2-EHn) (E = O, S (n = 1); N (n = 2)) under mild conditions to give M-Si-E-C-N (E = O, N), W-Si-N-C-S, and M-E-C-N (E = S, N) metallacycles depending on the metal M or heteroatom E. These three kinds of metallacycles were characterized by spectroscopy, elemental analysis, and X-ray crystallography. The first two silametallacycles take on some silylene complex character and are considered to form via (aryl)silylene complex intermediates generated by cleavage of the Si-C(aryl) bond in the eta(3)-alpha-silabenzyl ligand of 1-Mo and 1-W.

  DOI：

  10.1021/acs.organomet.5b00335
• 作为产物：
  描述：

  Cp*(CO)₂WMe(Py) 、 tris(p-tolyl)silane 在 三苯基硼烷 作用下， 以 甲苯 为溶剂， 反应 1.0h， 以52%的产率得到(η⁵-C₅Me₅)W(CO)₂{η³(Si,C,C)-Si(p-tolyl)₃}
  参考文献：
  名称：

  Direct Conversion of a Si–C(aryl) Bond to Si–Heteroatom Bonds in the Reactions of η³-α-Silabenzyl Molybdenum and Tungsten Complexes with 2-Substituted Pyridines

  摘要：

  eta(3)-alpha-Silabenzyl complexes Cp*M(CO)(2)-{eta(3)(Si,C,C)-Si(p-Tol)(3)} (M = Mo (1-Mo), W (1-W)) reacted with 2-substituted pyridines NC5H4(2-EHn) (E = O, S (n = 1); N (n = 2)) under mild conditions to give M-Si-E-C-N (E = O, N), W-Si-N-C-S, and M-E-C-N (E = S, N) metallacycles depending on the metal M or heteroatom E. These three kinds of metallacycles were characterized by spectroscopy, elemental analysis, and X-ray crystallography. The first two silametallacycles take on some silylene complex character and are considered to form via (aryl)silylene complex intermediates generated by cleavage of the Si-C(aryl) bond in the eta(3)-alpha-silabenzyl ligand of 1-Mo and 1-W.

  DOI：

  10.1021/acs.organomet.5b00335

文献信息

• (η³-α-Silabenzyl)tungsten Complexes: An Isolable Intermediate for Interconversion between a Silylene Complex and a Silyl Complex through 1,2-Aryl Migration
  作者：Eiji Suzuki、Takashi Komuro、Yuto Kanno、Hiromi Tobita

  DOI：10.1021/om4000105

  日期：2013.2.11

  eta(3)-alpha-Silabenzyl complexes Cp*W - (CO)(2)eta(3)(Si,C,C)-Si(p-Tol)(2)R} (1a, R = Me; 1b, R = p-Tol; Cp* = eta(5)-C5Me5, p-Tol = p-tolyl), the first silicon analogues of eta(3)-benzyl complexes, were synthesized by abstraction of DMAP (4-(dimethylamino)pyridine) with BPh3 either from (aryl)(DMAP.silylene)tungsten complexes 2a,b at room temperature or from (arylsilyl)(DMAP)tungsten complexes 3a,b under irradiation. Complex I was demonstrated to be a key intermediate for the interconversion between 2 and 3 and to serve as a synthetic equivalent for both base-free silylene complexes and coordinatively unsaturated silyl complexes.