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有机化学
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有机化学 ›› 2010, Vol. 30 ›› Issue (03): 345-358. 上一篇    下一篇

综述与进展

金属有机化合物中金属-配体键能的研究进展

曾青*,a，李祖成b，何家骐b   

  1. (a北京中医药大学中药学院基础教学部 北京 100102)
    (b南开大学化学系元素有机化学国家重点实验室 天津 300071)
  • 收稿日期:2008-07-30 修回日期:2009-07-27 发布日期:2010-03-28
  • 通讯作者: 曾青 E-mail:zq68315@yahoo.com.cn
  • 基金资助:

    国家级.973计划

Progress of Metal-Ligand Bonding Energetics in
Organometallic Compounds

Zeng Qing*,a,Li Zuchengb,He Jiaqib   

  1. (a Basic Course Teaching Department, School of Chinese Pharmacy, Beijing University of Chinese Medicine,
    Beijing 100102)
    (b State Key Laboratory of Elemento-Organic Chemistry, Department of Chemistry, Nankai University, Tianjin 300071)
  • Received:2008-07-30 Revised:2009-07-27 Published:2010-03-28
  • Contact: Zeng Qing E-mail:zq68315@yahoo.com.cn

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被引次数

4

介绍了金属有机物质热力学研究的进展, 概述了过渡金属-配体键能的基本概念、估测方式、实验和理论研究方法. 收集了已测得的第三副族到第八族所有中性金属有机络合物金属-配体σ-单键绝对键焓的实验值. 对第三副族及锕系元素, 收集了钪-氢、钪-碳、钍-氢、钍-碳、钍-氮、钍-氧、钍-硫、钍-氯、铀-氢、铀-碳、铀-硅、铀-氧、铀-氯、铀-溴、铀-碘、钐-氢、钐-碳、钐-硅、钐-氮、钐-磷、钐-氧、钐-硫、钐-氯、钐-溴和钐-碘键的键焓. 对第四副族元素, 收集了钛-碳、锆-氢、锆-碳、锆-硅、锆-氮、锆-氧、锆-氯、锆-碘、铪-氢、铪-碳键的键焓. 对第五副族元素, 收集了钒-氢、钽-碳键的键焓. 对第六副族元素, 收集了铬-氢、铬-碳、铬-硅、铬-氮、铬-氙、钼-氢、钼-碳、钼-硅、钼-氮、钼-磷、钼-氯、钼-溴、钼-碘、钼-氙、钨-氢、钨-碳、钨-硅、钨-氮、钨-氩、钨-氪、钨-氙键的键焓. 对第七副族元素, 收集了锰-氢、锰-碳、锰-硅、锰-氧、锰-硫、锰-氯、锰-溴、锰-碘、锝-氯、锝-溴、锝-碘、铼-氢、铼-碳、铼-氯、铼-溴、铼-碘键的键焓. 对第八族元素, 收集了铁-氢、铁-碳、铁-氮、铁-氩、铁-氪、铁-氙、钌-氢、钌-碳、钌-磷、锇-氢、锇-碳、钴-氢、钴-碳、铑-氢、铑-碳、铱-氢、铱-碳、铱-氯、铱-溴、铱-碘、镍-碳、镍-硫、钯-碳、铂-氢、铂-碳键的键焓. 但未包括平均键焓值. 此外, 还收集了铁-氢、铁-碳、铁-氮、铁-磷、铁-羰基、铁-亚硝基、铁-氧分子、铁-硼、铁-铝、铁-镓、铁-铟、铁-铊键的理论计算值以及金属有机片断和离子的键焓.

关键词: 金属有机化合物, 键能, 键焓, 键强

The present survey covers the literature through the end of April in 2009. The progress in the thermodynamic investigation of organometallic substances has been introduced since 1887. The basic concepts, the evaluation ways, the experimental and theoretical research methods of transition metal-ligand bond energies are summarized. The available experimental values of absolute transition metal-ligand σ-bond enthalpies of neutral organometallic complexes from group 3 to 10 are collected completely. In Group 3 and actinides, Sc-H, Sc-C, Th-H, Th-C, Th-N, Th-O, Th-S, Th-Cl, U-H, U-C, U-Si, U-O, U-Cl, U-Br, U-I, Sm-H, Sm-C, Sm-Si, Sm-N, Sm-P, Sm-O, Sm-S, Sm-Cl, Sm-Br and Sm-I bond enthalpies are included. In Group 4, Ti-C, Zr-H, Zr-C, Zr-Si, Zr-N, Zr-O, Zr-Cl, Zr-I and Hf-H, Hf-C bond enthalpies are collected. In Group 5, V-H and Ta-C bond enthalpies are collected. In Group 6, Cr-H, Cr-C, Cr-Si, Cr-N, Cr-Xe, Mo-H, Mo-C, Mo-Si, Mo-N, Mo-P, Mo-Cl, Mo-Br, Mo-I, Mo-Xe, W-H, W-C, W-Si, W-N, W-Ar, W-Kr and W-Xe bond enthalpies are included. In Group 7, Mn-H, Mn-C, Mn-Si, Mn-O, Mn-S, Mn-Cl, Mn-Br, Mn-I, Tc-Cl, Tc-Br, Tc-I, Re-H, Re-C, Re-Cl and Re-Br, Re-I bond enthalpies are collected. From Group 8 to 10, Fe-H, Fe-C, Fe-N, Fe-Ar, Fe-Ke, Fe-Xe, Ru-H, Ru-C, Ru-P, Os-H, Os-C, Co-H, Co-C, Rh-H, Rh-C, Ir-H, Ir-C, Ir-Cl, Ir-Br, Ir-I, Ni-C, Ni-S, Pd-C, Pt-H and Pt-C bond enthalpies are collected. But the data of mean bond dissociation enthalpies are not gathered. In addition, the calculated values of Fe-H, Fe-C, Fe-N, Fe-P, Fe-CO, Fe-NO, Fe-O2, Fe-B, Fe-Al, Fe-Ga, Fe-In and Fe-Tl bond energies are included. The bond dissociation enthalpies of organometallic fragments and ions are also collected thoroughly.

Key words: organometallic compound, bond energy, bond enthalpy, bond strength