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DFT study on the hydrogen bonds of phenol–cyclohexanone and phenol–H 2 O 2 in the Baeyer–Villiger oxidation
Author(s) -
Long Qingping,
Ji Hongbing,
Lv Shushen
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.21848
Subject(s) - cyclohexanone , chemistry , hydrogen bond , phenol , natural bond orbital , computational chemistry , acceptor , binding energy , hydrogen , crystallography , molecule , density functional theory , organic chemistry , catalysis , atomic physics , physics , condensed matter physics
Hydrogen bonds of phenol–cyclohexanone and phenol–H 2 O 2 in the studied Baeyer–Villiger (B–V) oxidation have been investigated by HF, B3LYP, and MP2 methods with various basis sets. The accurate single‐point energies were performed using CCSD(T)/6‐31+G(d,p) and CCSD(T)/aug‐cc‐pVDZ on the optimized geometries of MP2/6‐31+G(d,p). It has been confirmed that B3LYP/6‐31+G(d,p) could be used to study such hydrogen bonds. Energetic analysis of complexes was carried out using the Xantheas method with BSSE corrected by CP method. Orbital energy order (ε) illuminated that phenol with good hydrogen donor‐acceptor property can interact with cyclohexanone or H 2 O 2 to form hydrogen bound complexes, and the binding energies (BE ′ 2 ) range from −4.38 to −14.06 kcal mol −1 . NBO analysis indicated that the redistribution of atomic charges in the complexes facilitated nucleophilic attack of H 2 O 2 on cyclohexanone. The calculated results match remarkably well with the experimental phenomena. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009