The NBO charge distribution calculated at DFT level on the [LEX](+) species [LE = N,N'-dimethylbenzoimidazole2(3H)-thione (3) and -2(3H)-selone (4) (Scheme 1); X = I, Br] suggests that the most likely products from the reaction of 3 and 4 with IBr are the 10-X-2 charge-transfer (CT) adduct and the 10-Se-3 "T-shaped" hypervalent adduct featuring a linear Br-Se-I system, respectively. This prediction is confirmed by the synthesis, and X-ray diffraction analysis of 3 center dot IBr (I) and 4 center dot I0.72Br1.28 (II). In particular, II is a 10-Se-3 "T-shaped" hypervalent adduct containing an almost linear X-Se-X system [X-Se-X 179.07( 3)degrees, X = I-0.36/Br-0.64], which is roughly perpendicular to the average plane of the benzoimidazole moiety. The FT-Raman spectra of I and II agree very well with their structural features. In particular, the complexity of the FT-Raman spectrum of II reflects the disorder in the X-ray crystal structure of this compound.
DFT calculations, structural and spectroscopic studies on the products formed between IBr and N,N'-dimethylbenzoimidazole-2(3H)-thione and-2(3H)-selone / M.C. Aragoni, M. Arca, F. Demartin, F.A. Devillanova, A. Garau, F. Isaia, V. Lippolis, G. Verani. - In: DALTON TRANSACTIONS. - ISSN 1477-9226. - :13(2005), pp. 2252-2258.
|Titolo:||DFT calculations, structural and spectroscopic studies on the products formed between IBr and N,N'-dimethylbenzoimidazole-2(3H)-thione and-2(3H)-selone|
|Settore Scientifico Disciplinare:||Settore CHIM/03 - Chimica Generale e Inorganica|
|Data di pubblicazione:||2005|
|Digital Object Identifier (DOI):||http://dx.doi.org/10.1039/b503883a|
|Appare nelle tipologie:||01 - Articolo su periodico|