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Elucidating the hard/soft acid/base principle: a perspective based on half-reactions.
MedLine Citation:
PMID:  16729803     Owner:  NLM     Status:  PubMed-not-MEDLINE    
Abstract/OtherAbstract:
A comprehensive analysis is presented for the acid-base double-exchange reaction as well as the associated acid-displacement and base-displacement "half-reactions" with the goal of elucidating the meaning of the hard/soft acid/base (HSAB) principle and the conditions for its validity. When electron-transfer effects are important and other effects are negligible, the HSAB principle is driven by the surpassing stability of the soft acid/soft base product. When electrostatic effects dominate the reactivity, the HSAB principle is driven by the surpassing stability of the hard acid/hard base product. Because electron-transfer effects favor soft/soft interactions, while electrostatic effects favor hard/hard interactions, acid-base exchange reactions may be used to determine whether a reagent's reactivity is dominated by electron-transfer or by electrostatic effects. Because electron-transfer and electrostatic considerations separately favor the HSAB principle whenever the electronic chemical potentials of the acids and bases involved in the reaction are similar, our analysis provides strong support for the HSAB principle. The electronic chemical potential measures the intrinsic strength of acids and bases.
Authors:
Paul W Ayers; Robert G Parr; Ralph G Pearson
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Publication Detail:
Type:  Journal Article    
Journal Detail:
Title:  The Journal of chemical physics     Volume:  124     ISSN:  0021-9606     ISO Abbreviation:  J Chem Phys     Publication Date:  2006 May 
Date Detail:
Created Date:  2006-05-29     Completed Date:  2007-06-21     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  0375360     Medline TA:  J Chem Phys     Country:  United States    
Other Details:
Languages:  eng     Pagination:  194107     Citation Subset:  -    
Affiliation:
Department of Chemistry, McMaster University, Hamilton, Ontario L8S 4M1, Canada. ayers@mcmaster.ca
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