On the properties of Seâ¯N interaction: the analysis of substituent effects by energy decomposition and orbital interaction.
J Mol Model
; 22(1): 29, 2016 Jan.
Article
en En
| MEDLINE
| ID: mdl-26755190
ABSTRACT
The nature and strength of intermolecular Seâ¯N interaction between selenium-containing compounds HSeX (X = CH3, NH2, CF3, OCH3, CN, OH, NO2, Cl, F), and NH3 have been investigated at the MP2/aug-cc-pVDZ level. The Seâ¯N interaction is found to be dependent on the substituent groups, which greatly affect the positive electrostatic potential of Se atoms and the accepting electron ability of X-Se σ(∗) antibonding orbital. Energy decomposition of the Se â¯N interaction reveals that electrostatic and induction forces are comparable in the weak-bonded complexes and induction becomes more significant in the complexes with strong electron-withdrawing substituents. Natural bond orbital (NBO) analysis indicates that the primary source of the induction is the electron transfer from the N lone pair to the X-Se σ(∗) antibonding orbital. The geometry of the complex and the interaction directionality of NH3 to X-Se bond can be regarded as a consequence of the exchange-repulsion. The topological analysis on the electron density reveals the nature of closed-shell interaction in these X-Seâ¯N contacts. The Seâ¯N interaction in the complexes with the strong electron-withdrawing substituent has a partly covalent character.
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Base de datos:
MEDLINE
Idioma:
En
Revista:
J Mol Model
Asunto de la revista:
BIOLOGIA MOLECULAR
Año:
2016
Tipo del documento:
Article