Probing the Oxidation Chemistry of Half-Sandwich Iridium Complexes with Oxygen Atom Transfer Reagents

Abstract

The new complexes [Ir(Cp*)(phpy)3,5-bis(trifluoromethyl)benzonitrile](+) (1-NCAr(+)) and [Ir(Cp*)(phpy)(styrene)](+) (1-Sty(+), Cp* = η(5)-pentamethylcyclopentadienyl, phpy = 2-phenylene-κC(1')-pyridine-κN) were prepared as analogues of reported iridium water oxidation catalysts, to study their reactions with oxygen atom transfer (OAT) reagents at low temperatures. In no case was the desired product, an Ir(V)oxo complex, observed by spectroscopy. Instead, ligand oxidation was implicated. Oxidation of 1-NCAr(+) with the OAT reagent dimethyldioxirane (DMDO) yielded dioxygen when analyzed by GC, but formation of a heterogeneous or paramagnetic species was simultaneously observed. This amplifies uncertainty over the actual identity of iridium catalysts in the harsh oxidizing conditions required for water oxidation. Catalyst stability was then assessed for a reported styrene epoxidation mediated by [Ir(Cp*)(phpy)(OH2)](+) (1-OH2(+)). It was found that the OAT reagent iodosobenzene (PhIO) extensively oxidized the organic ligands of 1-OH2(+). Acetic acid was detected as a decomposition product. In addition, both the molecular structure and the aqueous electrochemistry of 1-OH2(+) are described for the first time. Oxidative scans revealed rapid decomposition of the complex. All of the above experiments indicate that degradation of the organic ligands in catalysts built with the Ir(Cp*)(phpy) framework are facile under oxidizing conditions. In separate experiments designed to promote ligand substitution, an unexpected silver-bridged, dinuclear Ir(III) species with terminal hydrides, [{Ir(Cp*)(phpy)H}2Ag](+) (2), was discovered. The source of Ag(+) for complex 2 was identified as AgCl.