Silver nanocluster redox-couple-promoted nonclassical electron transfer: an efficient electrochemical wolff rearrangement of α-diazoketones

Sudrik, Surendra G. ; Chaki, Nirmalya K. ; Chavan, Vilas B. ; Chavan, Sambhaji P. ; Chavan, Subhash P. ; Sonawane, Harikisan R. ; Vijayamohanan, K. (2006) Silver nanocluster redox-couple-promoted nonclassical electron transfer: an efficient electrochemical wolff rearrangement of α-diazoketones Chemistry - A European Journal, 12 (3). pp. 859-864. ISSN 0947-6539

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Official URL: http://onlinelibrary.wiley.com/doi/10.1002/chem.20...

Related URL: http://dx.doi.org/10.1002/chem.200500696

Abstract

In this work we report the unique electrocatalytic role of benzoic acid protected silver nanoclusters (Agn, mean core diameter 2.5 nm) in the Wolff rearrangement (Scheme 1) of α-diazoketones. More specifically, the presence of a Agn0/Agn+ redox couple facilitates a nonclassical electron-transfer process, involving chemical reaction(s) interposed between two electron-transfer steps occurring in opposite directions. Consequently, the net electron transfer between the electron mediator (Agn) and α-diazoketone is zero. In-situ UV-visible studies using pyridine as a nucleophilic probe indicate the participation of -ketocarbene/ketene as important reaction intermediates. Controlled potential coulometry of α-diazoketones using Agn as the anode results in the formation of Wolff rearranged carboxylic acids in excellent yield, without sacrificing the electrocatalyst.

Item Type:Article
Source:Copyright of this article belongs to John Wiley and Sons.
Keywords:Electrocatalysis; Electrochemistry; Electron Transfer; Ketocarbenes; Silver Nanoclusters
ID Code:68921
Deposited On:08 Nov 2011 04:40
Last Modified:08 Nov 2011 04:40

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