Probing 'spin-forbidden' oxygen-atom transfer: gas-phase reactions of chromium-porphyrin complexes.

ABSTRACT: Oxygen-atom transfer reactions of metalloporphyrin species play an important role in biochemical and synthetic oxidation reactions. An emerging theme in this chemistry is that spin-state changes can play important roles, and a 'two-state' reactivity model has been extensively applied especially in iron porphyrin systems. Herein we explore the gas-phase oxygen-atom transfer chemistry of meso-tetrakis(pentafluorophenyl)porphyrin (TPFPP) chromium complexes, as well as some other tetradentate macrocyclic ligands. Electrospray ionization in concert with Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry has been used to characterize and observe reactivity of the ionic species [(TPFPP)Cr(III)](+) (1) and [(TPFPP)Cr(V)O](+) (2). These are attractive systems to examine the effect

SUBMITTER: Crestoni ME 

PROVIDER: S-EPMC2863096 | biostudies-literature | 2010 Mar

REPOSITORIES: biostudies-literature