respectively. The Si−Cl bond length of 2.160(1) Å is longer than those typically observed (ca. 2.023 Å). Reaction of 2 with CO afforded Cp(dmpe)V(CO)2 (7) via homoleptic cleavage of the V−Si bond. The reaction of 5 with Li(Et2O)3B(C6F5)4 generated what appears to be the silylene complex [Cp(dmpe)VSiPh2]B(C6F5)4, on the basis of elemental analysis.
Cp(dmpe)VSiHRR'型
钒甲
硅烷基络合物是通过Cp(dmpe)VMe(1)与RR'SiH 2(2,R,R'= Ph; 3,R = Mes,R'= H室温下在苯中),同时释放出CH 4气体。这些络合物是顺磁性的,具有高自旋d 3构型,并显示出广泛的1 H NMR共振。它们具有三足形的钢琴凳几何形状,并且每个
硅原子采用四面体结构,没有有害的V··HSi相互作用。的V-Si键长度2是2.5629(8),和在V-P键长是2.4613(8)和2.4621(8)。Cp(dmpe)
VCH 2的反应的KIE值为2.1±0.1在室温下用Ph 2 SiH 2 / Ph 2 SiD 2制成Ph(4)。2与Ph 2 SiHCl在苯中的反应导致甲
硅烷基交换,以82%的收率得到Cp(dmpe)VSiClPh 2(5)。通过用Ph 3 CCl将5氧化,得到
钒(III)甲
硅烷基络合物,得到Cp(dmpe)V(Cl)SiClPh