高等学校化学学报 ›› 2005, Vol. 26 ›› Issue (8): 1517.

• 研究论文 • 上一篇    下一篇

氮分子与过渡金属中心钼、铁、钒相互作用的理论研究

金夕, 曹泽星, 张乾二   

  1. 厦门大学化学系, 固体表面物理化学国家重点实验室, 厦门361005
  • 收稿日期:2004-07-20 出版日期:2005-08-10 发布日期:2005-08-10
  • 通讯作者: 曹泽星(1962年出生),男,博士,教授,博士生导师,从事理论与计算化学研究.E-mail:zxcao@xmu.edu.cn E-mail:zxcao@xmu.edu.cn
  • 基金资助:

    国家自然基金(批准号:20173042,20233020,20021002);国家科技部(批准号:001CB1089,2004CB719902);教育部博士学科点基金资助.

A Theoretical Study of Interaction Between Dinitrogen and Single Transition-met al Centers Mo, Fe and V

JIN Xi, CAO Ze-Xing, ZHANG Qian-Er   

  1. State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, Xiamen University, Xiamen 361005, China
  • Received:2004-07-20 Online:2005-08-10 Published:2005-08-10

摘要: 通过密度泛函理论计算研究了过渡金属模型体系的二氮复合物(N2)M(NH2)3(NH3)和(N2)M(SH)3(NH3)(-OCH2COO-)(M=Mo,V,Fe),预测了质子-电子还原二氮过程的能量变化.计算结果表明,对于单过渡金属中心体系,钼与N2存在强的相互作用,钒与N2相互作用较弱,铁不能有效地结合N2.通过质子化过渡金属模型体系中高柠檬酸二齿配体的羧基氧,并改变金属中心的价态和体系的自旋态,可以调控羧基氧与金属配位键的生成与断裂.两类模型体系的计算结果显示,对于单过渡金属中心的钼、钒、铁体系,钼是结合N2最有效的活性位.

关键词: 二氮的成键与还原, 钼, 铁, 钒, DFT计算

Abstract: Complexes of the transition met al-containing model compounds with dinitrogen (N2)M(NH2)3(NH3) and (N2)M(SH)3(NH3)(-OCH2COO-) [MMo,V, Fe] were studied by the density functional theory. The relative energetics of the reduction of N2 to ammonia by the proton-electron transfer to the dinitrogen derivative was predicted. The calculated results show that there is a strong interaction between the Mo center and dinitrogen and the V…NN interaction is relatively weak, whereas the Fe center cannot bind N2. The homocitrate ring opening in the simplified Mo-containing fragment in the FeMoco was predicted to be manipulable by controlling the spin multiplicity and oxidation state of the transition met al complex. The present results from both models indicate that the Mo is the most efficient active site for the dinitrogen binding and reduction among the single transition-met al centers Mo, V and Fe.

Key words: Binding and reduction of dinitrogen, V, Mo, Fe, DFT calculation

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