[(η5-C5Me5)(CO)2W(SiPh2)(CCtBu)] | 855313-97-2

• 英文名称: [(η5-C5Me5)(CO)2W(SiPh2)(CCtBu)]
• 英文别名: [(η⁵-C₅Me₅)(CO)₂W(SiPh₂)(CC^tBu)]
• CAS: 855313-97-2
• 化学式: C₃₀H₃₄O₂SiW
• 分子量: 638.534
• InChiKey: QNAWXLFHWLXJLX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [(η5-C5Me5)(CO)2W(SiPh2)(CCtBu)] 、 丙酮 以 氘代甲苯 为溶剂， 以98%的产率得到
  参考文献：
  名称：

  η:η-Alkynyl-Bridged W−Si Complexes:  Formation, Structure, and Reaction with Acetone

  摘要：

  Reactions of (eta5-C5Me4R)(CO)2(MeCN)WMe (R = Me, Et) with HPh2SiCCtBu gave the novel alkynyl-bridged W-Si complexes, (eta5-C5Me4R)(CO)2W(mu-eta1:eta2-CCtBu)(SiPh2) (R = Me, Et), whose alkynyl ligands bridge the tungsten and silicon atoms in an eta1:eta2-coordination mode. The structures of these complexes were fully characterized, including X-ray crystallography. Treatment of (eta5-C5Me5)(CO)2W(mu-eta1:eta2-CCtBu)(SiPh2) with acetone resulted in acetone insertion into the silicon-alkynyl linkage followed by intramolecular C-H activation of the tBu group to give the chelate-type alkyl-alkene complex, (eta5-C5Me5)(CO)2W(eta1:eta2-CH2CMe2C=CHSiPh2OCMe2).

  DOI：

  10.1021/ja050441o
• 作为产物：
  描述：

  (3,3-dimethylbut-1-yn-1-yl)diphenylsilane 、 [(η⁵-C₅Me₅)(CO)₂W(NCMe)Me] 以 not given 为溶剂， 以63%的产率得到[(η5-C5Me5)(CO)2W(SiPh2)(CCtBu)]
  参考文献：
  名称：

  η:η-Alkynyl-Bridged W−Si Complexes:  Formation, Structure, and Reaction with Acetone

  摘要：

  Reactions of (eta5-C5Me4R)(CO)2(MeCN)WMe (R = Me, Et) with HPh2SiCCtBu gave the novel alkynyl-bridged W-Si complexes, (eta5-C5Me4R)(CO)2W(mu-eta1:eta2-CCtBu)(SiPh2) (R = Me, Et), whose alkynyl ligands bridge the tungsten and silicon atoms in an eta1:eta2-coordination mode. The structures of these complexes were fully characterized, including X-ray crystallography. Treatment of (eta5-C5Me5)(CO)2W(mu-eta1:eta2-CCtBu)(SiPh2) with acetone resulted in acetone insertion into the silicon-alkynyl linkage followed by intramolecular C-H activation of the tBu group to give the chelate-type alkyl-alkene complex, (eta5-C5Me5)(CO)2W(eta1:eta2-CH2CMe2C=CHSiPh2OCMe2).

  DOI：

  10.1021/ja050441o

文献信息

• Reactions of Tungsten Acetylide–Silylene Complexes with Pyridines: Direct Observation of Silylene/Silyl Migration in Tungsten Acetylide and Carbyne/Vinylidene Frameworks
  作者：Hiroyuki Sakaba、Hiroyuki Oike、Yasuhiro Arai、Eunsang Kwon

  DOI：10.1021/om300772c

  日期：2012.12.10

  Reaction of acetylide-silylene complex Cp*-(CO)(2)W(SiPh2)((CCBu)-Bu-t) (1a) with 4-(dimethylamino)-pyridine (DMAP) gave an equilibrium mixture of DMAP-stabilized silylene acetylide complexes trans- and cis-Cp*-(CO)(2)W(SiPh2 center dot DMAP)((CCBu)-Bu-t) (trans-4 and cis-4). The corresponding reaction using Cp*(CO)(2)W(SiPh2)(CCSiMe3) (2) produced the novel DMAP-coordinated silenylcarbyne/silylvinylidene complex Cp*(CO)(2)W[CC(SiPh2 center dot DMAP)(SiMe3)] (6a) as a major product, which was equilibrated with trans- and cis-Cp*(CO)(2)W(SiPh2 center dot DMAP)(CCSiMe3) (trans-5a and cis-5a) via silylene/silyl migration. The novel structures of cis-4 and 6a were revealed by X-ray crystallography. A mixture of 2 and pyridine exhibited interesting temperature-dependent NMR spectral changes, indicating the formation of trans- and cis-Cp*(CO)(2)W(SiPh2 center dot py)(CCSiMe3) (trans-5b and cis-5b) and Cp*(CO)(2)W[CC(SiPh2 center dot py)(SiMe3)] (6b) at low temperature, while a mixture of la and pyridine showed no such spectral changes.