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Reactions of Arenediazonium o ‐Benzenedisulfonimides with Aliphatic Triorganoindium Compounds
Author(s) -
Barbero Margherita,
Cadamuro Silvano,
Dughera Stefano,
Ghigo Giovanni
Publication year - 2008
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200700931
Subject(s) - chemistry , hydrazone , tautomer , nucleophile , formaldehyde , nitrogen atom , medicinal chemistry , double bond , reaction mechanism , salt (chemistry) , computational chemistry , density functional theory , diazonium compounds , aryl , ring (chemistry) , organic chemistry , catalysis , alkyl
The reaction of various arenediazonium o ‐benzenedisulfonimides with aliphatic triorganoindium compounds is described. Surprisingly, with triethyl‐ or tributylindium we obtained N ‐ethyl‐ or N ‐butylanilines, respectively. This is the first case in which, at least formally, the reactive site of a diazonium salt is the nitrogen atom directly bonded to the aromatic ring. In contrast, with trimethylindium we obtained only formaldehyde (aryl)hydrazones. In order to explain the difference between trimethyl‐ and triethylindium we have proposed some reaction mechanisms, supported by detailed density functional (DFT) calculations. The possible role of diazene/hydrazone tautomerism initially assumed was discarded and therefore three mechanisms for the key step (nucleophilic addition of the trialkylindium to the N=N double bond of diazene) were studied. For the favoured mechanism there is a difference in the energy barriers of 2 kcal mol –1 between the reactions with trimethyl‐ and triethylindium. This difference is explained on the basis of the different C–In bond energies in the two organometallics and it is assumed to be enough to explain their different behaviour under the experimental conditions.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)