Activation of the Si–H bond of Et2SiH2 in photochemical reaction with W(CO)6: Spectroscopic characterization of intermediate W–Si compounds and the revisited crystal structure of the bis{(μ-η2-hydridodiethylsilyl)tetracarbonyltungsten(I)} complex [{W(μ-η2-H–SiEt2)(CO)4}2]
作者:Agnieszka Gądek、Andrzej Kochel、Teresa Szymańska-Buzar
DOI:10.1016/j.jorganchem.2007.05.027
日期:2007.8
(1JSi–H = 43 Hz, 2JSi–H = 34 Hz, 1JW–H = 40 Hz) was assigned to the agostic proton of the W(η2-H–SiEt2) group in the most stable compound isolated from the photochemical reaction products in crystalline form. The molecular structure of the bis(μ-η2-hydridodiethylsilyl)tetracarbonyltungsten(I)} complex [W(μ-η2-H–SiEt2)(CO)4}2] was established by single-crystal X-ray diffraction studies. The tungsten hydride
W(CO)6与二乙基硅烷的光化学反应已用于生成稳定性变化的新型钨硅化合物。最初形成的η 2 -硅烷中间体配合物[W(CO)5(η 2 -H-SiHEt 2)],其特征在于两个相等强度的双重带2 Ĵ H-H = 10在赫兹δ = 5.10(1 Ĵ硅-H = 217 Hz)和δ = -8.05(1 J W–H = 38 Hz,1 J Si–H = 93 Hz),通过1 H NMR光谱法(甲基环己烷-d14,-10°C)。该η 2 -硅烷复合物转化在黑暗中给予更多的稳定的品种。其中之一的特征是两个等强度的质子信号 在δ = -8.25和-10.39 ppm时以2 J H–H = 5.2 Hz的双峰形式观察到。δ = −9.31处的单线质子共振,侧接29个Si和183 W卫星(1 J Si–H = 43 Hz,2 J Si–H = 34 Hz,1 J W–H = 40 Hz)的质子的W(η