Nucleophilic displacement at the benzoyl centre: A study of the change in geometry at the carbonyl carbon atom

Colthurst, Matthew J. and Williams, A. (1997) Nucleophilic displacement at the benzoyl centre: A study of the change in geometry at the carbonyl carbon atom. Journal of the Chemical Society-Perkin Transactions 2 (8). pp. 1493-1497. ISSN 0300-9580. (The full text of this publication is not available from this repository)

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Abstract

The second-order rate constants for the reaction between hydroxide ion and phenoxide ion with 4-nitrophenyl esters of substituted benzoic acids in 10% acetonitrile-water (v/v) solution obey Hammett sigma correlations, The values of the Hammett rho of 1.67 (k(ArO)) and 2.14 (k(OH)) are consistent with a large change in hybridization at the central carbon by comparison with the rho value for a standard reaction where a full sp(2) to sp(3) change occurs, The transition state for the concerted reaction thus has a substantially tetrahedral geometry, The observation of the anti-Hammond effect whereby the rho value for the hydroxide ion exceeds that of the less reactive phenoxide ion is consistent with a concerted, A(N)D(N), mechanism for these reactions, A stepwise mechanism, A(N) + D-N, is unlikely to yield a measurable break in the Hammett correlation for a change in the benzoyl substituent if the partitioning of the putative tetrahedral intermediate involves forward and reverse reactions with Hammett correlations possessing similar rho values.

Item Type: Article
Depositing User: T. Nasir
Date Deposited: 29 Oct 2009 20:09
Last Modified: 30 Jun 2014 09:34
Resource URI: http://kar.kent.ac.uk/id/eprint/18359 (The current URI for this page, for reference purposes)
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