蝎型钒氧配合物Tp*VO(OOCHCCHCOOCH_3)(pz*H)和Tp*VO(DMSO)(NCS)的合成、结构及量子化学研究

Synthesis,Structure and Quantum Chemistry of Scorpionates Oxovanadium Compleses:Tp*VO(OOCHCCHCOOCH_3)(pz*H) and Tp*VO(DMSO)(NCS)

本文在室温条件下,甲醇体系中,设计并首次合成了2种蝎型半夹心钒氧配合物Tp*VO(OOCHCCHCOOCH3)(pz*H)(1)和Tp*VO(DMSO)(NCS)(2)(Tp*=三聚3,5-二甲基吡唑硼酸根),通过元素分析、红外光谱对配合物进行了表征,利用X-射线单晶衍射方法对晶体结构进行了测定,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1和2的稳定性相近,且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 half-sandwich monomeric complexes of oxovanadium（Ⅳ）？ Tp＊VO（OOCHCCHCOOCH3）（pz＊H）（1） and Tp＊VO（DMSO）（NCS）（2）（Tp＊=hydrotris（3,5-dimethylpyrazolyl）borate,pz＊H=3,5-dimethylpyrazole） have been synthesized from the reaction of VOSO4·nH2O with respective ligands.The complexes were characterized by element analysis,IR spectra and single crystal X-ray diffraction.The electronic structure and the bonding characters of the two complexes were analyzed with ab initio calculations.The calculations results showed that the structural stability of complexes 1 and 2 are close.The atomic net charge distribution in the molecular system indicates obvious covalent interaction between the coordinated atoms（N,O） and vanadium.The results are consistent with the structural analysis of complexes.