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Type: Artigo de periódico
Title: Marked changes in relative nucleophilicity in comparing S(N)2Ar reactions of free arenes and coordinated arenes. Kinetic studies of reactions of (eta(6)-chlorobenzene)(eta(5)-cyclopentadienyl)iron(II) tetrafluoroborate with anionic and neutral nucleophiles
Author: Gomes, PCB
Vichi, EJS
Moran, PJS
Neto, AF
Maroso, ML
Miller, J
Abstract: Quantitative kinetic studies have be en made of reactions of the (eta(6)-chlorobenzene)(eta(5)-cyclopentadienyl)iron(II) cation, (C6H5Cl)Fe(C5H5)(+) (1), With methoxide, phenoxide, methanethiolate, benzenethiolate, and azide ions in methanol, piperidine, morpholine, aniline, and thiourea in methanol, and guanidine in ethanol. The results were compared with the same nucleophile-solvent combinations in reactions with 1-chloro-2,4-dinitrobenzene, C6H3(NO2)(2)Cl (2). In general, the reactivity decreases on passing from 2 to 1. The decrease is small (less than or equal to 10(-1)) for phenoxide (PhO(-)), methanethiolate (MeS(-)), and guanidine (gua) and large (ca. 10(-5)) for benzenethiolate (PhS(-)), azide (N-3(-)), piperidine (pip), morpholine (morph), aniline (anil), and thiourea (thiou). The differences in reactivity when comparing the S(N)2Ar reactions of 1 and 2 is discussed in terms of the different location of the negative charge generated in the transition state by the electrons displaced from the reaction center by the entering groups (arenide electrons).
Editor: Amer Chemical Soc
Rights: fechado
Identifier DOI: 10.1021/om9601817
Date Issue: 1996
Appears in Collections:Artigos e Materiais de Revistas Científicas - Unicamp

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