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Type: Artigo de periódico
Title: Spectroscopic and theoretical studies of some 2-substituted N-methoxy-N-methyl-amides
Author: Olivato, PR
Gomes, RD
Rodrigues, A
Domingues, NLC
Rittner, R
Dal Colle, M
Abstract: B3LYP/6-311++G(3df,3pd) calculations along with the NBO analysis of some 2-substituted N-methoxy-N-methyl-amides Y-C(R)(2)C(O)N(OMe)Me [Y = Br 1, SEt 2, SePh 4 (for R = H) and SEt 3 (for R = Me)] indicated the existence of three conformers for 1, 2, 4, namely one cis (c) and two gauche (g(1), g(2)), and two gauche (g(1), g(2)) forms for 3. The g(1) conformer is the most stable and the least polar for all derivatives, while the c one is the most polar for 1, 2 and 4. As far as the stability is concerned, the g(2) conformer is more abundant with respect to the c one for compounds 1 and 2, and slightly less stable than c for 4. For the derivative 3, the g(1) conformer is more stable and slightly less polar than the g(2) one. Moreover, the computed (nu(co)) frequencies and the relative populations of the two forms correlate quite well with the IR (nu(co)) doublet frequency components and their relative intensities in solution. The occurrence of Fermi resonance in the fundamental nu(co) region, in solution, precludes the estimative of the relative populations of the c, g(1), g(2) conformers for 1, 2 and 4. NBO analysis showed that the n(N) -> pi(center dot)(co) orbital interaction is the main factor which stabilizes the gauche (g(1), g(2)) conformers into a larger extent relative to the cis (c) one for 1, 2, 4. For these compounds along with the 3 derivative, the same interaction stabilizes more the g(1) conformer than the g(2) one. The sum of the orbital interactions from NBO analysis and the trend of the electrostatic interactions justifies quite well the populations of the (c) and gauche (g(1), g(2)) conformers for 1, 2 and 4, along with the (g(1), g(2)) conformers populations for 3 found in the gas phase. (C) 2012 Elsevier B.V. All rights reserved.
Subject: Conformational analysis
Infrared spectroscopy
Theoretical calculations
2-Substituted N-methoxy-N-methyl amides
Country: Holanda
Editor: Elsevier Science Bv
Citation: Journal Of Molecular Structure. Elsevier Science Bv, v. 1031, n. 91, n. 103, 2013.
Rights: fechado
Identifier DOI: 10.1016/j.molstruc.2012.07.005
Date Issue: 2013
Appears in Collections:Unicamp - Artigos e Outros Documentos

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