Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2010-02-01

A theoretical study of dihydrogen bonds in small protonated rings: aziridine and azetidine cations.

B G Oliveira, R C M U Araújo, A B Carvalho, M N Ramos

Index: Spectrochim. Acta. A. Mol. Biomol. Spectrosc. 75(2) , 563-6, (2010)

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Abstract

B3LYP/6-311++G(d,p) calculations were used to predict some molecular properties of the C2H6N+...BeH2, C2H6N...MgH2, C3H8N...BeH2 and C3H8N+...MgH2 dihydrogen-bonded complexes. In these systems, it was demonstrated that the C2H6N+ and C3H8N+ protonated rings are potential candidates to bind with protonic hydrogens derived from alkaline earth metal compounds, BeH2 and MgH2. In terms of structural parameters and quantification of the dihydrogen bond energies, we should mention that the C2H6N+ three-membered ring provides the formation of stronger bound systems, which are 4.0 kJ mol-1 more stables than C3H8N+ four-membered ones. As complement, the analysis of the infrared spectrum indicated that red-shifts and blue-shifts are occurring in the N-H bonds of both C2H6N+ and C3H8N+ cationic rings. However, these two vibrational shifts were also verified on BeH2 and MgH2, what lead us to affirm that cationic compounds derived from small nitrogen rings and earth alkaline molecules are able to form unusual dihydrogen-bonded complexes by means of distinct spectroscopic phenomena, the red-shits and blue-shifts.Copyright (c) 2009 Elsevier B.V. All rights reserved.