Mass Spectrometry and Gas‐phase Ion Chemistry of Metal–phenolate and Metal–phenol complexes

Abstract

The current chapter summarizes 276 references to offer an up‐to‐date survey of literature on the mass spectrometry and gas‐phase ion chemistry of phenolate‐ or phenol‐containing metal complexes and their chalcogenide thio‐ and seleno‐analogs. Analytical applications of MS techniques to the characterization of these metal–ligand systems are discussed. The latter include more than 400 species such as mixed‐ligand metal complexes, bifunctional compounds containing organometallic and classical Werner‐type coordination sites, nanoclusters, species with metal–metal bonds, mixed‐metal complexes, etc. Some of them are isomers. The reviewed data provides the reader with a solid foundation for selecting the adequate MS instrumentation in related future studies. Data on gas‐phase ion structure, energetics and reactivity are summarized as well. Circa 150 examples of ion/molecule reactions with the participation of metal‐containing ions and phenol or thiophenol derivatives are examined. Additionally, the review addresses the 3D structural features of several model complexes between metal ions and phenol‐ or thiophenol‐related species as determined from theoretical calculations and IRMPD spectroscopic measurements, as well as their use for elucidation of the nature of metal cation–π interaction or σ‐binding, which mimic the active centers of biomolecular systems.