Gas-phase studies of copper(I)-mediated CO2 extrusion followed by insertion of the heterocumulenes CS2 or phenylisocyanate

Abstract

The gas-phase extrusion–insertion reactions of the copper complex [bathophenanthroline (Bphen)CuI(O2CC6H5)]2−, generated via electrospray ionization, was studied in a linear ion trap mass spectrometer with the combination of collision-induced dissociation (CID) and ion-molecule reaction (IMR) events. Multistage mass spectrometry (MSn) experiments and density functional theory (DFT) demonstrated that extrusion of carbon dioxide from [(Bphen)Cu(O2CC6H5)]2− (CID) gives the organometallic intermediate [(Bphen)Cu(C6H5)]2−, which subsequently reacts with carbon disulfide (IMR) via insertion to yield [(Bphen)Cu (SC(S)C6H5)]2−. The fragmentation of the product ion resulted in the formation of [Bphen..