The reaction of WOCl4 with 2,4-di-tert-butyl-6-((isopropylamino)methyl)phenol followed by the reaction with phenyl isocyanate leads to the formation of imidotungsten(VI) complex [W(NPh)Cl3(OC6H3(CH2NH-i-Pr)-2-t-Bu2-4,6)] 4 with a chelating aminophenolate ligand. When the same procedure was applied using aminophenols with bulkier substituents in the amino group, the final product was an unexpected Schiff-base complex [W(NPh)Cl3(OC6H3(CHNPh)-2-t-Bu2-4,6)] 5, where the ligand is derived from 2,4-di-tert-butyl-6-((phenylimino)methyl)phenol. Complex 5 is also formed in the thermal degradation of 4. On the whole, 5 appears to be formed by a disproportionation of intermediate compounds, which are analogous to complex 4. The solid-state structures of 4 and 5 have been determined by X-ray crystallography whereas the solution structures were studied by 1H and 13C NMR.
WOCl4 与 2,4-二叔丁基-6-((异丙基
氨基)甲基)
苯酚反应,然后与
异氰酸苯酯反应,生成了带有螯合
氨基苯酚配体的
亚胺钨(VI)络合物 [W(NPh)Cl3(OC6H3(CH2NH-i-Pr)-2-t-Bu2-4,6)] 4。当使用
氨基中取代基较多的
氨基苯酚进行同样的处理时,最终产物是一种意想不到的席夫碱配合物 [W(NPh)Cl3(OC6H3(CHNPh)-2-t-Bu2-4,6)] 5,其中的
配体来自 2,4-二叔丁基-6-((苯基亚
氨基)甲基)
苯酚。总体而言,5 似乎是由中间化合物歧化形成的,与复合物 4 类似。4 和 5 的固态结构是通过 X 射线晶体学确定的,而溶液结构则是通过 1H 和 13C NMR 研究的。