ePrints

Direct studies on 5-coordinate intermediates formed during substitution at tetrahedral Fe sites: Role of bound nucleophile in labilisation of leaving group

Lookup NU author(s): Brendan Garrett, Professor Richard Henderson

Downloads

Full text for this publication is not currently held within this repository. Alternative links are provided below where available.

Abstract

The substitution reactions of the tetrahedral Fe sites in [FeCl 4]-, [Fe2S2Cl4] 2-, [Fe4S4Cl4]2- and [{MoFe3S4Cl3}2(-SEt) 3]3- with 4-RC6H4S- (R = MeO, Me, H, Cl or NO2) all involve rapid binding of the thiolate to a Fe site and formation of a kinetically and spectroscopically detectable intermediate. Kinetic studies allow calculation of the rate of Fe-Cl dissociation from the 5-coordinate site of the intermediate (k2R). The rate of Fe-Cl dissociation from the intermediate exhibits a marked dependence on the nature of the bound thiolate with log 10(k2R) increasing in a linear manner with the calculated NBO charge on the sulfur atom of the coordinated thiolate. This behaviour indicates that Fe-Cl bond dissociation at the 5-coordinate intermediate involves a process in which Fe-thiolate bond shortening occurs prior to movement of the Fe-Cl bond. © The Royal Society of Chemistry 2007.

Publication metadata

Author(s): Garrett B, Henderson RA

Publication type: Article

Publication status: Published

Journal: Dalton Transactions

Year: 2007

Issue: 31

Pages: 3435-3439

Date deposited: 05/07/2010

ISSN (print): 1477-9226

ISSN (electronic): 1477-9234

Publisher: Royal Society of Chemistry

URL: http://dx.doi.org/10.1039/b706272a

DOI: 10.1039/b706272a

Altmetrics

Share