Sakaba Hiroyuki, Yoshida Mako, Kabuto Chizuko, Kabuto Kuninobu
Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai, Japan.
J Am Chem Soc. 2005 May 25;127(20):7276-7. doi: 10.1021/ja050441o.
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).
（η⁵-C₅Me₄R）（CO）₂（MeCN）WMe（R = Me，Et）与HPh₂SiCCtBu反应生成了新型的炔基桥连的W-Si配合物（η⁵-C₅Me₄R）（CO）₂W（μ-η¹:η²-CCtBu）（SiPh₂）（R = Me，Et），其炔基配体以η¹:η²配位模式桥连钨原子和硅原子。这些配合物的结构通过包括X射线晶体学在内的方法进行了全面表征。用丙酮处理（η⁵-C₅Me₅）（CO）₂W（μ-η¹:η²-CCtBu）（SiPh₂）会导致丙酮插入硅-炔基键中，随后叔丁基发生分子内C-H活化，生成螯合型烷基-烯烃配合物（η⁵-C₅Me₅）（CO）₂W（η¹:η²-CH₂CMe₂C=CHSiPh₂OCMe₂）。
