Mechanistic investigation of halopentaaquachromium(III) complexes: Comparison of computational and experimental results

K.M. Uddin; D. Ralph; D.J. Henry

doi:10.1016/j.comptc.2015.08.007

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Mechanistic investigation of halopentaaquachromium(III) complexes: Comparison of computational and experimental results

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Mechanistic investigation of halopentaaquachromium(III) complexes: Comparison of computational and experimental results

K.M. Uddin, D. Ralph and D.J. Henry

Computational and Theoretical Chemistry, Vol.1070, pp.152-161

2015

DOI: https://doi.org/10.1016/j.comptc.2015.08.007

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Abstract

The mechanism for the substitution reactions of halopentaaquachromium(III) complexes in the series, [CrX(H2O)5]2+, where X = F−, Cl−, Br−, or I− have been investigated using density functional theory. Several different mechanistic pathways were explored including associative interchange (Ia), dissociative (D) and the associatively activated dissociation mechanisms (Da). The lowest overall activation enthalpy (ΔH‡) obtained for the fluoride system is for the Ia pathway, with immediate proton abstraction leading to the formation of HF and the conjugate base. For the chloride, bromide and iodide systems the Da pathway has the lowest ΔH‡ values. Activation enthalpies determined at the PBE0/cc-pVDZ level, in aqueous solution (PCM), are in excellent agreement with the experimental results (MAD is 1.0 kJ mol−1). Reaction profiles were analyzed in terms of activation volumes to explain the observed trends.

Details

Title: Mechanistic investigation of halopentaaquachromium(III) complexes: Comparison of computational and experimental results
Authors/Creators: K.M. Uddin (Author/Creator) - Murdoch University
D. Ralph (Author/Creator) - Murdoch University
D.J. Henry (Author/Creator) - Murdoch University
Publication Details: Computational and Theoretical Chemistry, Vol.1070, pp.152-161
Publisher: Elsevier BV
Identifiers: 991005542417807891
Copyright: © 2015 Elsevier B.V.
Murdoch Affiliation: School of Engineering and Information Technology
Language: English
Resource Type: Journal article

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Citation topics: 2 Chemistry; 2.22 Inorganic & Nuclear Chemistry; 2.22.1258 Catalytic Complexes
Web Of Science research areas: Chemistry, Physical
ESI research areas: Chemistry