Studies on nitrosation reagents and nitrosation reactions using the frontier-orbital approach

Abstract

The structure and reactivity of some nitrosation reagents (⁺NO, H₂O–⁺NO, ON–Cl, ON–SCN, and ON–OH) are discussed on the basis of Gaussian 80 calculations and Klopman's polyelectronic perturbation theory for closed shell systems. Geometrical optimization and total energy calculations reveal that nitrosation by nitrite in aqueous acid solution probably occurs via a nitrosyl cation–water complex, in which the nitrosyl group is bound to water by the Coulomb interaction. The found reactivity of the nitrosation reagents is used to elucidate the observed reactivity in nitrosation of thiols, sulphides, thiocarbonyls, alcohols, and amines.