Fragmentation Mechanisms of Glycine-Cu+ in the Gas Phase. An Experimental and Theoretical Study

Abstract

Electrosprayed copper complexes of glycine (GlyCu+) were formed from a glycine/CuX2 (X = Cl, CH3CO2) mixture, in methanol. The collision-induced fragmentation of the most abundant isotopic form Gly63Cu+ was studied as a function of collision energy. Four fragment ions are observed: 63CuNHCH2+, 63Cu+, CH2NH2+, plus a minor loss of H2O. The potential energy surface for formation of these fragment ions has been investigated at the B3LYP/6-311+G(2d,2p)//B3LYP/6-31G* level. Several types of mechanisms were considered, involving either metal insertion into covalent bonds (C−C, C−O, and C−N) or dissociative attachment whereby the metal ion catalyzes the fragmentation by its distant electronic influence. Mechanisms starting with copper insertion into the C−C bond account for the most favorable pathways for the formations of CuNHCH2+ and CH2NH2+. Dissociative attachment cannot be excluded to participate to the formation of CuNHCH2+ and is the only way to explain H2O loss. Finally, calculations on the possible mech...