Stabilization of Aliphatic and Aromatic Diazonium Ions by Coordination: An Experimental and Theoretical Study

FAVIO DOCTOROBICH; NATALIA ESCOLA; CECILIA TRÁPANI; DARÍO A. ESTRIN; MARIANO C. GONZÁLEZ LEBRERO; ADRIÁN G. TURJANSKI

ORGANOMETALLICS

Año: 2000 p. 3810 - 3817

0276-7333

  The reaction of [Ru(bpy)2(NO)Cl]2+ and [Fe(CN)5NO]2- with n-butylamine has been studiedas a plausible route for obtaining aliphatic diazonium ions stabilized by coordination. Thesereactions yield a variety of products originating mainly by direct attack of nucleophiles onthe intermediate carbocation (or diazonium ion) and by rearrangement of the carbocationor the diazonium ion. The ratio of unrearranged to rearranged products can be taken as anexperimental measurement of the stabilization of the diazonium ions. DFT-computed resultssuggest that the stabilization by complexation of the diazonium ions is larger in theironpentacyano complex, in agreement with the fact that no rearrangement products areobserved in the reaction of this species with n-butylamine.