Mass spectrometric characterization of high-valent metal-oxo, -peroxo and -peroxy intermediates of relevance in oxidation processes

The coupling of mass spectrometry with ionization techniques like electrospray ionization (ESI) or matrix-assisted matrix-assisted laser desorption-ionization (MALDI) offers many advantages over other well-established spectroscopic techniques employed for the investigation of intermediates or short-lived species in condensed-phase. In this review we describe some of the applications of mass spectrometry, in particular of ESI-MS to the detection and characterization of high-valent metal-oxo, -peroxo and -peroxy derivatives, crucial intermediates in the oxyfunctionalization of organic substrates. In addition, by utilizing gas-phase ion-molecule reactions and MS/MS experiments, information on the intrinsic reactivity of the short-lived intermediates may be obtained. The combined use of ESI-MS in association with other spectroscopic techniques and theoretical calculations is discussed as well. © 2006 Wiley Periodicals, Inc.