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Chiral discrimination in hydrogen‐bonded complexes of 2‐methylol oxirane with hydrogen peroxide
Author(s) -
Zhang Guiqiu,
Yin Aixia,
Chen Dezhan
Publication year - 2008
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.21878
Subject(s) - chemistry , diastereomer , hydrogen bond , enantiomer , molecule , chirality (physics) , binding energy , stereochemistry , basis set , computational chemistry , intermolecular force , interaction energy , polarizability , crystallography , organic chemistry , chiral symmetry breaking , symmetry breaking , physics , quantum mechanics , nuclear physics , nambu–jona lasinio model
A systematic quantum chemical study reveals the effects of chirality on the intermolecular interactions between two chiral molecules bound by hydrogen bonds. The methods used are second‐order Møller–Plesset perturbation theory (MP2) with the 6‐311++g(d,p) basis set. Complexes via the OH···O hydrogen bond formed between the chiral 2‐methylol oxirane (S) and chiral HOOH (P and M) molecules have been investigated, which lead to four diastereomeric complexes. The nomenclature of the complexes used in this article is enantiomeric configuration sign corresponding to English letters. Such as: sm, sp. The relative positions of the methylol group and the hydrogen peroxide are designated as syn (same side) and anti (opposite side). The largest chirodiastaltic energy was Δ E chir = −1.329 kcal mol −1 [9% of the counterpoise correct average binding energy D e (corr)] between the sm‐syn and sp‐anti in favor of sm‐syn. The largest diastereofacial energy was −1.428 kcal mol −1 between sm‐syn and sm‐anti in favor of sm‐syn. To take into account solvents effect, the polarizable continuum model (PCM) method has been used to evaluate the chirodiastaltic energies, and diastereofacial energies of the 2‐methylol oxirane···HOOH complexes. The chiral 2,3‐dimethylol oxirane (S, S) is C 2 symmetry which offers two identical faces. Hence, the chirodiastaltic energy is identical to the diastereomeric energy, and is Δ E chir = 0.563 kcal mol −1 or 5.3% of the D e (corr) in favor of s,s‐p. The optimized structures, interaction energies, and chirodiastaltic energies for various isomers were estimated. The harmonic frequencies, IR intensities, rotational constants, and dipole moments were also reported. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009