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Singlet methylene insertion into polar OH and NH bonds of water and ammonia—Ab initio and DFT study
Author(s) -
Ramasami K.,
Ramalingam M.,
Venuvanalingam P.,
Jaccob M.
Publication year - 2010
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.22236
Subject(s) - chemistry , methylamine , ab initio , basis set , singlet state , ammonia , methylene , hydrogen bond , ab initio quantum chemistry methods , transition state , computational chemistry , ylide , density functional theory , molecule , stereochemistry , medicinal chemistry , catalysis , atomic physics , organic chemistry , physics , excited state
Abstract Correlated ab initio molecular orbital, DFT, QCISD, G3MP2, and QCISD(T) calculations have been used to investigate the geometries, energetics, and mechanisms governing the insertion reactions of 1 CH 2 into OH and NH bonds of water and ammonia, respectively, in gas phase adopting 6‐311++g(d, p) basis set. It is found that 1 CH 2 reacts with water and ammonia to produce the ylide‐like intermediates H 2 COH 2 and H 2 CNH 3 , which in turn undergo 1,2‐hydrogen shift to produce methanol and methylamine, respectively. Results obtained indicate that in the gas phase, the ylides and the transition states are located below the reactants' energy levels. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010