Reaction of VCl₃ with bis[N-(2,6-diisopropylphenyl)imino]acenaphthene (dpp-bian) in air afforded [VOCl₂(dpp-bian)] (1). The complex was characterized by IR and UV-vis spectroscopies and elemental analysis. The crystal structure of 1 was determined by X-ray diffraction (XRD) analysis. The vanadium atom is in a square-pyramidal OCl₂N₄ coordination environment. The cyclic voltammogram (CV) in dichloromethane reveals an irreversible oxidation process at +1.40 V (vs. Ag/AgCl) assigned to the V(IV)/V(V) couple, and two consecutive quasi-reversible one-electron reduction processes at −0.32 V and −1.05 V (vs. Ag/AgCl), respectively, assigned to the bian/bian^−/˙ and bian^−/˙/bian²⁻ couples, followed by irreversible reduction at −1.6 V (vs. Ag/AgCl). The EPR spectrum of 1 in toluene shows a single 8-line signal typical for oxidovanadium(IV) complexes with d¹ configuration. The magnetic behavior of 1 confirms the presence of one unpaired electron (μ_eff (330 K) = 1.67 μ_B), and the isolation of the paramagnetic centers. Application of 1 to oxidation of alkanes documented high catalytic activity under mild conditions. The kinetics and selectivity of alkane oxygenation by the 1/H₂O₂ and 1/PCA/H₂O₂ systems (PCA is pyrazine-2-carboxylic acid) were studied. The reaction is more efficient in the presence of PCA.

中文翻译：

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具有BIAN配体的新型氧化钒（iv）配合物：合成，结构，氧化还原性质和催化活性†

VCl ₃与双[ N-（2,6-二异丙基苯基）亚氨基] ac（dpp-bian）在空气中反应，得到[VOCl ₂（dpp-bian）]（1）。该复合物通过IR和UV-可见光谱法和元素分析来表征。通过X射线衍射（XRD）分析确定1的晶体结构。钒原子处于方形金字塔形的OCl ₂ N ₄配位环境中。在二氯甲烷中的循环伏安图（CV）揭示了一种不可逆的氧化工艺在1.40 V（相对于分配给V（银/氯化银）IV）/ V（V）耦合和分别在-0.32 V和-1.05 V（相对于Ag / AgCl）的两个连续的准可逆单电子还原过程分配给bian / bian- ^/ ˙和bian- ^/ ˙/ bian ^2-耦合，然后在-1.6 V时不可逆还原（相对于Ag / AgCl）。甲苯中的1的EPR谱图显示了具有d ¹构型的氧化钒（IV）配合物的单个8线信号。的磁性行为1次确认一个不成对电子的存在（μ _EFF（330 K）= 1.67 μ_乙），以及顺磁中心的隔离。1在烷烃氧化中的应用证明在温和的条件下具有很高的催化活性。研究了通过1 / H ₂ O ₂和1 / PCA / H ₂ O ₂系统（PCA为吡嗪-2-羧酸）进行烷烃氧化的动力学和选择性。在PCA存在下，该反应更有效。