高等学校化学学报

高等学校化学学报 ›› 1993, Vol. 14 ›› Issue (6): 831.

• 研究论文 • 上一篇    下一篇

过渡金属双核化合物Cr2(O2CH)4、Mo2(O2CH)4及CrMo(O2CH)4的从头计算研究

龚良发, 张明瑜   

  1. 吉林大学理论化学研究所, 理论化学计算国家重点实验室, 长春 130023
  • 收稿日期:1992-07-03 修回日期:1993-02-24 出版日期:1993-06-24 发布日期:1993-06-24
  • 通讯作者: 张明瑜
  • 基金资助:

    国家自然科学基金

Ab initio Study on Transition Metal Binuclear Complexes MM'(O2CH)4(M,M'=Cr, Mo)

GONG Liang-Fa, ZHANG Ming-Yu   

  1. Institute of Theoretical Chemistry, Jilin Unitvrsity, Stale Key Laboratory of Computational Theoretical Chemistry, Changchun, 130023
  • Received:1992-07-03 Revised:1993-02-24 Online:1993-06-24 Published:1993-06-24

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摘要： 用从头计算方法研究双核过渡金属化合物Cr2(O2CH)4、MO2(O2CH)4及CrMo(O2CH)4的金属—金属多重键性质,计算优化键长与实验值符合很好,原子布居表明Mo2(O2CH)4和CrMo(O2CH)4中Mo—Mo、Cr—Mo键分别为σ2π4δ2与σ2δ2π4四重键,同时金属-d与氧和碳-p电子间的电荷重叠对分子稳定有相当贡献。对Cr2(O2CH)4在优化键长下3种组态σ2δ2δ2σ2、π4π4及σ2δ2π4的电子结构、原子布居、总能量及电离能的计算进行比较,讨论了Cr—Cr的成键性质,指出描述Cr—Cr间金属多重键本质必须考虑电子相关效应的影响。

关键词: 金属&mdash, 金属多重键, 基函数, 从头算, 原子布居, 电子相关

Abstract: In this paper, the ab initio calculations are performed on the metal-metal multiple bonds of the binuclear transition metal complexes MM'(O2CH)4, namely, Cr2(O2CH)4, Mo2(O2CH)4 and CrMo(O2CH)4. The optimized bond lengthes are in good agreement with the experimental values.The calculated results indicate that the Mo-Mo and Cr-Mo bonds are quadruple bonds which correspond to the configurations σ2π4δ2 and σ2δ2π4 in Mo2(O2CH)4 and CrMo(O2CH)4, respectively.For Cr2(O2CH)4, the bonding property of Cr-Cr bond is explored by comparing the calculated results of three configurations.It is shown that a more rigorous theoretical calculation is needed in order to correctly describe the Cr-Cr multiple bonding essence.

Key words: Meral-metal multiple bond, Basis function, Ab initio, Atomic population, Electron correlation

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