Document Details

Document Type : Article In Journal 
Document Title :
Cu(bipy)2+/TEMPO-catalyzed oxidation of alcohols: Radical or nonradical mechanism?
Cu(bipy)2+/TEMPO-catalyzed oxidation of alcohols: Radical or nonradical mechanism?
 
Subject : Chemistry 
Document Language : English 
Abstract : In the oxidation of alcohols with TEMPO as catalyst, the substrate has alternatively been postulated to be oxidized but uncoordinated TEMPO+ (Semmelhack) or Cu-coordinated TEMPO• radical (Sheldon). The reaction with the Cu(bipy)2+/TEMPO cocatalyst system has recently been claimed, on the basis of DFT calculations, to not be a radical reaction but to be best viewed as electrophilic attack on the alcohol C-Hα bond by coordinated TEMPO+. This mechanism combines elements of the Semmelhack mechanism (oxidation of TEMPO to TEMPO+) and the Sheldon proposal ("in the coordination sphere of Cu"). The recent proposal has been challenged on the basis of DFT calculations with a different functional, which were reported to lead to a radical mechanism. We carefully examine the results for the two functionals and conclude from both the calculated energetics and from an electronic structure analysis that the results of the two DFT functionals are consistent and that both lead to the proposed mechanism with TEMPO not acting as radical but as (coordinated) positive ion. 
ISSN : 0020-1669 
Journal Name : Inorganic Chemistry 
Volume : 50 
Issue Number : 23 
Publishing Year : 1432 AH
2011 AD 
Article Type : Article 
Added Date : Sunday, March 11, 2012 

Researchers

Researcher Name (Arabic)Researcher Name (English)Researcher TypeDr GradeEmail
Paola BelanzoniBelanzoni, Paola ResearcherDoctorate 
Carine MichelMichel, Carine ResearcherDoctorate 
Evert Jan BaerendsBaerends, Evert JanResearcherDoctoratee.j.baerends@vu.nl

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