18281-22-6Relevant academic research and scientific papers
Reactions of arenediazonium o-benzenedisulfonimides with aliphatic triorganoindium compounds
Barbero, Margherita,Cadamuro, Silvano,Dughera, Stefano,Ghigo, Giovanni
scheme or table, p. 862 - 868 (2009/04/11)
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 kcalmol-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, 2008.
