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学科主题: 药学
题名:
A theoretical approach to the leaving ligand problem of photosubstitution reactions of hexacoordinate transition metal mixed-ligand complexes
作者: Zhang, TL1; Jin, DM1
刊名: INDIAN JOURNAL OF CHEMISTRY SECTION A-INORGANIC BIO-INORGANIC PHYSICAL THEORETICAL & ANALYTICAL CHEMISTRY
发表日期: 2001-08-01
卷: 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
Citation statistics:
内容类型: 期刊论文
URI标识: http://ir.bjmu.edu.cn/handle/400002259/52487
Appears in Collections:北京大学药学院_期刊论文

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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

Recommended Citation:
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.
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