Vanadium(V) imido complexes are widely used in olefin polymerization and oligomerization. In this report we present the synthesis and the results of ethylene polymerization studies for a series of vanadium(V) imido complexes with various substituents at the imido fragment. All complexes have been prepared in nearly quantitative yields by the interaction of N-sulfinylamines with VOCl₃ or VO(OnPr)₃ and characterized using ¹H, ¹³C, ⁵¹V NMR and elemental analysis. The solid-state structure of complex V(=NAr_OMe)(OnPr)₃ was established using X-ray. Vanadium(V) imido chlorides and n-propoxides exhibited similar moderate catalytic activities (320–547 kg_PE·mol(V)⁻¹·h⁻¹·atm⁻¹). The maximum catalytic activity (547 kg_PE·mol(V)⁻¹·h⁻¹·atm⁻¹) was achieved for (adamantylimido)vanadium(V) n-propoxide. The molecular weights of the resulting polyethylenes were higher (M_v = 3.7–6.5·10⁵ Da) for imido n-propoxide complexes as compared to the corresponding imido chlorides (M_v = 2.1–5.5·10⁵ Da). The localization of DFT calculated HOMO on imide nitrogen was proposed to favor the reaction between imide ligand and Et₂AlCl used as activator.

钒（V）亚氨基配合物广泛用于烯烃聚合和低聚反应。在本报告中，我们介绍了一系列在亚氨基片段上具有各种取代基的钒（V）亚氨基配合物的合成和乙烯聚合反应的研究结果。通过N-亚磺酰基胺与VOCl ₃或VO（O n Pr）₃的相互作用，可以几乎定量地制备所有络合物，并使用¹ H，¹³ C，⁵¹ V NMR和元素分析对其进行表征。使用X射线建立了复合物V（= NAr _OMe）（O n Pr）₃的固态结构。钒（V）亚氨基氯化物和正丙醇盐表现出类似适度的催化活性（320-547千克_PE ·摩尔^（V）-1 · ħ ^-1 ·大气压^-1）。对于（金刚烷酰亚胺基）钒（V）正丙醇，达到了最大催化活性（547 kg _PE · mol（V）^-1 · h ^-1 · atm ^-1）。所得聚乙烯的分子量较高（M _v  = 3.7-6.5 · 10 ⁵道尔顿）为亚氨基正丙氧基络合物相比于相应的亚氨基氯化物（M _v = 2.1–5.5 · 10 ⁵ Da）。提出了用DFT计算的HOMO在酰亚胺氮上的定位，以促进酰亚胺配体与用作活化剂的Et ₂ AlCl之间的反应。