PNNL

Abstract

Collision-induced dissociations of the Ag+(methanol)n complexes for n = 1 - 4 are studied using kinetic energy dependent guided ion beam tandem mass spectrometry. In all cases, the primary products are endothermic loss of an intact neutral ligand from the complex. The cross section thresholds are interpreted to yield 0 and 298 K bond dissociation energies (BDEs) after accounting for the effects of multiple ion-molecule collisions, internal energy of the complexes, and unimolecular decay rates. These values are compared with theoretical values obtained using high level ab initio calculations. Generally good agreement is found except for the third ligand. The nature of the bonding in these complexes and their BDEs are examined in detail. Although the effect is not as dramatic as in singly or doubly ligated copper complexes, 5s-4ds hybridization found in the Ag+(methanol)n complexes, n = 1 and 2, enhances the BDEs.