Kinetic and the thermodynamic aspects of the CT and T-shaped adduct formation between 1,3-dimethylimidazoline-2-thione (-2-selone) with halogens
ARAGONI, MARIA CARLA;ARCA, MASSIMILIANO;ISAIA, FRANCESCO;LIPPOLIS, VITO
2006-01-01
Abstract
The reactions between L=E donors [L: 1,3-dimethylimidazolyl framework; E: S (1), Se (2)] and halogens X2 (X: Cl, Br, I) to form either “T-shaped” hypervalent chalcogen (TY) or linear charge-transfer-type adducts (CT) have been studied in the density functional theory (DFT) context by considering both thermodynamic and kinetic aspects. Apart from the case of the adducts between sulfur donors and diiodine, hypervalent compounds are calculated to be always more stable than CT ones in the gas phase, in agreement with the experimental results based on spectroscopic and structural determinations. NBO and FMO analyses suggest explanations for this. Reaction mechanism studies reveal that CT adducts are always the first products of the reactions and no transition states connecting the reactants directly to TY adducts have been found. The present calculations indicate that, at least for 1 and 2, TY adducts are obtained from CT adducts and not directly from the reactants.File | Size | Format | |
---|---|---|---|
EJIC 2006.pdf Solo gestori archivio
Type: versione editoriale
Size 220.61 kB
Format Adobe PDF
|
220.61 kB | Adobe PDF | & nbsp; View / Open Request a copy |
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.