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A theoretical approach to the leaving ligand problem of photosubstitution reactions of hexacoordinate transition metal mixed-ligand complexes
Zhang, TL1; Jin, DM1
刊名INDIAN JOURNAL OF CHEMISTRY SECTION A-INORGANIC BIO-INORGANIC PHYSICAL THEORETICAL & ANALYTICAL CHEMISTRY
2001-08-01
40期:8页:793-803
收录类别SCI
文章类型Article
WOS标题词Science & Technology
类目[WOS]Chemistry, Multidisciplinary
研究领域[WOS]Chemistry
关键词[WOS]PHOTOCHEMICAL SUBSTITUTION-REACTIONS ; TETRAGONAL CHROMIUM(III) COMPLEXES ; RELATIVE QUANTUM YIELDS ; PREDICTING PHOTOREACTIONS ; ORGANOMETALLIC COMPLEXES ; COORDINATION-COMPOUNDS ; ELECTRONIC SPECTRA ; PHOTOPHYSICS ; PHOTOLYSIS ; STATE
英文摘要

A coordination theory approach to the specific site labilization in ligand photosubstitution reactions has been proposed for hexacoordinate mixed-ligand transition metal complexes. On the basis of molecular orbital theory and the ligand even-distribution assumption, the relative stability of a metal-ligand bond in an excited species is expressed as a function of molecular orbital energy gap resulting from sigma and pi interactions between the metal and ligands, and of the Jahn-Teller effects of the ground and excited species. In terms of the function, some experimental facts have been analyzed. It is likely that the alteration in the electron-pair number upon excitation accounts for the difference between the d(3) type (including d(1-3) and weak field d(4)) and strong field d(6) type (including strong field d(4-7)) complexes in the leaving ligand character. The a and pi interactions may act differently, or even oppositely, on the leaving ligand. The impact of sigma interaction on the leaving ligand has also been assessed for complexes with other electronic configurations.

语种英语
WOS记录号WOS:000170539300001
引用统计
文献类型期刊论文
条目标识符http://ir.bjmu.edu.cn/handle/400002259/52487
专题北京大学药学院
作者单位1.Henan Inst Chem, Zhengzhou 450004, Peoples R China
2.Beijing Univ, Sch Pharmaceut Sci, Dept Bioinorgan Chem, Beijing 100083, Peoples R China
推荐引用方式
GB/T 7714
Zhang, TL,Jin, DM. A theoretical approach to the leaving ligand problem of photosubstitution reactions of hexacoordinate transition metal mixed-ligand complexes[J]. INDIAN JOURNAL OF CHEMISTRY SECTION A-INORGANIC BIO-INORGANIC PHYSICAL THEORETICAL & ANALYTICAL CHEMISTRY,2001,40(8):793-803.
APA Zhang, TL,&Jin, DM.(2001).A theoretical approach to the leaving ligand problem of photosubstitution reactions of hexacoordinate transition metal mixed-ligand complexes.INDIAN JOURNAL OF CHEMISTRY SECTION A-INORGANIC BIO-INORGANIC PHYSICAL THEORETICAL & ANALYTICAL CHEMISTRY,40(8),793-803.
MLA Zhang, TL,et al."A theoretical approach to the leaving ligand problem of photosubstitution reactions of hexacoordinate transition metal mixed-ligand complexes".INDIAN JOURNAL OF CHEMISTRY SECTION A-INORGANIC BIO-INORGANIC PHYSICAL THEORETICAL & ANALYTICAL CHEMISTRY 40.8(2001):793-803.
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