Author(s) Raymond, O.; Bühl, M.; Lane, J.R.; Henderson, W.; Brothers, P.J.; Plieger, P.G.
Journal Inorg Chem
Date Published 2020 Feb 17

Structures of aqueous [Be(HO)], its outer-sphere and inner-sphere complexes with F, Cl, and SO, and dinuclear complexes with a [Be(κ-OH)(κ-SO)] core have been studied through Car-Parrinello molecular dynamics (CPMD) simulations with the BLYP functional. According to constrained CPMD/BLYP simulations and pointwise thermodynamic integration, the free energy of deprotonation of [Be(HO)] and its binding free energy with F are 9.6 and -6.2 kcal/mol, respectively, in good accord with available experimental data. The computed activation barriers for replacing a water ligand in [Be(HO)] with F and SO, 10.9 and 13.6 kcal/mol, respectively, are also in good qualitative agreement with available experimental data. These ligand-substitution reactions are indicated to follow associative interchange mechanisms with backside (S2-like) attack of the anion relative to the aquo ligand it is displacing. Outperforming static density functional theory computations of the salient kinetic and thermodynamic quantities involving simple polarizable continuum solvent models, CPMD simulations are validated as a promising tool for studying the structures and speciation of beryllium complexes in aqueous solution.

DOI 10.1021/acs.inorgchem.9b03309
ISSN 1520-510X
Citation Raymond O, Bühl M, Lane JR, Henderson W, Brothers PJ, Plieger PG. Molecular Dynamics Investigation of Beryllium Complexes. Inorg Chem. 2020;59(4):2413-2425.

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