Reduction of Acetonitrile by Hydrated Magnesium Cations Mg+ (H2 O)n (n≈20-60) in the Gas Phase.

Abstract

Ion-molecule reactions of Mg+ (H2 O)n (n≈20-60) with CH3 CN are studied by Fourier-transform ion-cyclotron resonance mass spectrometry. Collision with CH3 CN initiates the formation of MgOH+ (H2 O)n-1 together with CH3 CHN. or CH3 CNH. , which is similar to the reaction of hydrated electrons (H2 O)n - with CH3 CN. In subsequent reaction steps, three more CH3 CN molecules are taken up by the clusters, to form MgOH+ (CH3 CN)3 after a reaction delay of 60 seconds. Density functional theory (DFT) calculations at the M06/6-31++G(d,p) level of theory suggest that the bending motion of CH3 CN allows the unpaired electron that is solvated out from the Mg center to localize in a π*(CN)-like orbital of the bent CH3 CN.- , which undergoes spontaneous proton transfer to form CH3 CNH. or CH3 CHN. , with the former being kinetically more favorable. The reaction energy for a cluster with the hexacoordinated Mg center is more exothermic than that with the pentacoordinated Mg. The CH3 CNH. or CH3 CHN. is preferentially solvated on the cluster surface rather than at the first solvation shell of the Mg center. By contrast, the three additional CH3 CN molecules taken up by the resulting MgOH+ (H2 O)n clusters coordinate directly to the first solvation shell of the MgOH+ core, as revealed by DFT calculations.