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Intramolecular nonbonding interactions in organoseleniums: quantification using a computational thermochemical approach

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Title Intramolecular nonbonding interactions in organoseleniums: quantification using a computational thermochemical approach
 
Creator ROY, DIPANKAR
SUNOJ, RB
 
Subject density functional theory
intramolecular mechanics
molecular configurations
orbital calculations
 
Description Intramolecular Se···O nonbonding interactions in a series of ortho-formylarylselenides (O···Se–Y, with Y = –Me, –Ph, –CN, –Cl, and –F) are quantified using density functional theory. Two methods based on the relative stabilities of various conformers are employed in evaluating the strength of intramolecular interactions. These methods, namely, cis–trans (CT) and thermodynamic cycle (TDC), depends on the energy changes associated with conformational interconversion, where the nonbonding interaction is turned on or off (respectively, in cis and trans conformer). The strength of interactions are found to be dependent on the nature of Se–Y acceptor orbitals and follows the order Me ~ Ph < CN < Cl < F. Natural Bond Orbital (NBO) analysis using DFT methods points to nO→σSe–Y* electron delocalization as the key contributing factor towards Se···O nonbonding interaction. Examination of the topological properties of the electron density with the Atoms-in-Molecule (AIM) method reveals that the electron density at the Se···O bond critical point exhibits a fairly good correlation with the nonbonding interaction energies estimated using the CT and TDC methods.
 
Publisher Elsevier
 
Date 2009-03-05T08:23:51Z
2011-11-25T18:34:39Z
2011-12-26T13:07:06Z
2011-12-27T05:55:08Z
2009-03-05T08:23:51Z
2011-11-25T18:34:39Z
2011-12-26T13:07:06Z
2011-12-27T05:55:08Z
2007
 
Type Article
 
Identifier Journal of Molecular Structure: THEOCHEM 809(1-3), 145-152
0166-1280
http://dx.doi.org/10.1016/j.theochem.2007.01.022
http://hdl.handle.net/10054/872
http://dspace.library.iitb.ac.in/xmlui/handle/10054/872
 
Language en