Intramolecular Halogen Atom Coordinated H Transfer via Ion-Neutral Complex in the Gas Phase Dissociation of Protonated Dichlorvos Derivatives.

Intramolecular halogen atom coordinated H transfer reaction in the gas phase dissociation of protonated dichlorvos derivatives has been explored by electrospray ionization tandem mass spectrometry. Upon collisional activation, protonated dichlorvos underwent dissociation reaction via cleavage of the P-O bond to give reactive ion-neutral complex (INC) intermediate, [dimethoxylphosphinoylium + dichloroacetaldehyde]. Besides direct dissociation of the complex, intramolecular chlorine atom coordinated H transfer reaction within the complex takes place, leading to the formation of protonated dimethyl chlorophosphate. To investigate the fragmentation mechanism, deuterium-labeled experiments and several other halogen-substituted (Br and F) analogs of dichlorvos were prepared and evaluated, which display a similar intramolecular halogen transfer. Density functional theory (DFT)-based calculations were performed and the computational results also support the mechanism. Graphical Abstract ᅟ.