金属有机化合物中金属-配体键能的研究进展

Progress of Metal-Ligand Bonding Energetics in Organometallic Compounds

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.

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 con- cepts, 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 a-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-C1, U-H, U-C, U-Si, U-O, U-CI, U-Br, U-I, Sm-H, Sm-C, Sm-Si, Sm-N, SIn-P, Sin-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, Hf-H and 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-C1, Mn-Br, Mn-I, Tc-C1, Tc-Br, Tc-I, Re-H, Re-C, Re-C1, Re-Br and 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-C1, 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 dissocia- tion enthalpies of organometallic fragments and ions are also collected thoroughly.