首页   按字顺浏览 期刊浏览 卷期浏览 The Chelate, Cryptate and Macrocyclic Effects
The Chelate, Cryptate and Macrocyclic Effects

 

作者: RobertD. Hancock,   ArthurE. Martell,  

 

期刊: Comments on Inorganic Chemistry  (Taylor Available online 1988)
卷期: Volume 6, issue 5-6  

页码: 237-284

 

ISSN:0260-3594

 

年代: 1988

 

DOI:10.1080/02603598808072293

 

出版商: Taylor & Francis Group

 

数据来源: Taylor

 

摘要:

The chelate, macrocyclic, and cryptate effects are analyzed. It is concluded that for all three effects considerable stabilization is derived from the greater basicity induced in donor atoms as ethylene bridges are added. Further considerations of importance in these effects are (1) desolvation effects, where steric constraints to solvation of the donor atoms in the free ligand lead to increased complex stability, (2) enforced dipole-dipole repulsion in the ligand, which is relieved on complex formation, and (3) structural preorganization of the ligand such that the donor atoms in the free ligand are already correctly oriented for complex formation. Only for the chelate effect is entropy of paramount importance, where it is derived from a cratic effect. It is emphasized that the level of preorganization of macrocycles, and to a lesser extent cryptands, is much lower than commonly realized. Newly emerging types of more highly preorganized ligands are discussed.

 

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