异羟肟酸氧钒化合物的合成表征及配位化学性质研究

Synthesis,characterization and coordination chemistry of vanadium(Ⅳ)hydroxamate complex

分别以不同的异羟肟酸为配体,合成了3个氧钒(Ⅳ)配合物,运用元素分析、红外光谱、核磁共振谱(1HNNR,13CNMR,51VNMR)、电子顺磁共振和电子吸收光谱等测试手段对配合物进行了表征.分别在不同的羟基醇中以氧钒(Ⅳ)配合物BHAOV为基础,合成了2个含烷氧基的五价氧钒(Ⅴ)化合物.在吡啶中合成了含吡啶的六配位氧钒(Ⅳ)配合物BHAOV(PY),V占据第6位置S原子,可使其不被氧原子进攻而氧化,要使V内层发生氧化,在四价钒上至少有一个空的配位位点是完全必要的.而且还研究了BHAOV在乙腈中的配位反应动力学.

Three vanadyl(Ⅳ)compounds containing different aromatic monoylhydroxamic acid have been synthesized and characterized by elemental analyses,NMR(~1H NNR,^(13) C NMR,^(51)V NMR),IR,EPR and UV-vis spectroscopies.In alcohols,a variety of V(Ⅴ) analogs BHAOV(OR)(R=-CH_3,-C_2H_5)are formed by aerial oxidation.A six-coordinate V(Ⅳ)pydine adduct BHAOV(PY)can be formed and this undergoes oxidation to V(Ⅴ)complexes much more slowly,demonstrating that a vacant coordinate site is required for the coordination of O_2 to VO(BHA)_2 before inner-sphere oxidation can take place.The coordination kinetics of BHAOV in CH_3CN is studied with UV-vis spectroscopy.