蝎型钒氧苯甲酸配合物的合成、结构及量化计算  

Synthesis,Structure and Quantum Chemistry Calculation of Scorpionate Oxovanadium Complexes with Benzoate

作　　者：李章朋[1] 邢永恒[1] 张元红[1] 白凤英[1] 曾小庆[2] 葛茂发[2] 

机构地区：[1]辽宁师范大学化学化工学院,辽宁大连116029 [2]中国科学院化学研究所,北京100190

出　　处：《物理化学学报》2009年第4期741-746,共6页Acta Physico-Chimica Sinica

基　　金：国家自然科学基金(20771051,20633050);辽宁省教育厅2007年度创新团队计划(2007T093)资助

摘　　要：设计合成了两种以聚吡唑硼酸盐、苯甲酸为配体的钒氧配合物VO[HB(pz)3](pzH)(C6H5COO)(1)和VO[HB(3,5-Me2pz)3](3,5-Me2pzH)(C6H5COO)(2)((HB(pz)3:聚吡唑硼酸钠盐;pzH:吡唑;HB(3,5-Me2pz)3:聚甲基吡唑硼酸钠盐;3,5-Me2pzH:3,5-二甲基吡唑).通过元素分析、红外光谱和X射线单晶衍射方法对配合物进行了表征.并结合从头计算结果进一步分析了配合物的稳定性及分子中配键的共价特征.分析结果表明,配合物2的稳定性大于配合物1,中心钒原子周围的价键类型都属于共价键范畴,键序分析结果与晶体结构测定的键长结果是一致的.Two new monomeric complexes of oxovanadium （IV）,VO[HB（pz）3]（pzH）（C6H5COO） （1） and VO[HB（3,5-Me2pz）3]（3,5-Me2pzH）（C6H5COO） （2） （HB（pz）3：hydrotris（pyrazolyl）borate; pzH：pyrazole; HB（3,5-Me2pz）3：hydrotris （3,5-dimethylpyrazolyl）borate; 3,5-Me2pzH：3,5-dimethyl pyrazole） were synthesized from the reaction of VOSO4· nH2O with corresponding ligands. The complexes were characterized by elemental analysis,IR spectrum,and single crystal X-ray diffraction. The electronic structures and the bonding characteristics of both complexes were analyzed using ab initio calculations. Calculation results show that the structure of complex 2 is more stable than that of complex 1. The atomic net charge distribution in the molecular system indicates obvious covalent interaction between the coordinated atoms and vanadium. These results are consistent with the structural analyses of these complexes.

关 键 词：钒氧配合物 聚吡唑硼酸盐 晶体结构 量子化学 

分 类 号：O627.53[理学—有机化学]