A Strategy for Generating Naked‐Metal Clusters for Gas‐Phase Reactivity Studies by FTICR–MS

Abstract

Cluster reactivity in the gas phase has been probed extensively with clusters generated by using a variety of custombuilt sources. These include pulsed-laser vaporisation, continuous-operation ovens, fast-atom and secondary-ion sputtering, dc discharge, and pulsed-arc cluster-ion sources.[1] All generate an assortment of clusters of different nuclearities, and MS n techniques make selection of a particular sized cluster relatively straightforward. Both homo-and heteronuclear clusters are known.[2] All of these techniques employ a similar strategy to cluster synthesis; that is, the target is vaporised, the gas-phase metal atoms condensed, and the resulting clusters examined by mass spectrometry. We report herein an entirely different approach for the production of bare-metal gas-phase clusters, in which presynthesised transition-metal-carbonyl-cluster anions are delivered into the gas phase by a standard electrospray ionisation (ESI) source and stripped free of ligands by using collision-induced dissociation (CID) at the skimmer cone. The benefits of this approach are high yields of a specific cluster, no requirement for a special source, easy access to heteronuclear clusters and/ or those with interstitial atoms, and a vast library of known clusters to draw from.Because mixed-metal-carbonyl clusters are currently extensively used as precursors for metal nanoparticle catalysts (the clusters are absorbed inside mesoporous silica and calcined to remove the ligands), [3] examination of their gasphase reactivity may provide insight into their action as[*] Dr.

Historical Perspectives in the Study of Ion Chemistry by Mass Spectrometry: From the Gas Phase to Solution

“…Other related examples are the synthesis of naked metal clusters using a ligand-stripping process of ESI-generated [CoRu 3 (CO) 13 ] À to get [CoRu 3 ] À from McIndoes group [271] and the gas-phase preparation of organomagnesates [196] and organocuprates [227] by OHair.…”

Mass Spectrometric Investigations of the Dissociation of [C@W6Cl17]− Ions in the Gas Phase

“…In these experiments 2 2− and the cluster ion [C@W 6 Cl 17 ] − ( 3 − ; which is formed after loss of Cl − ) are transferred into the gas phase entirely, without any initial decomposition. Thus, the decomposition of 3 − can be observed step by step in different isolation and collisionally activated dissociation (CAD) experiments 13…”