Iridium mediated methyl and phenyl C–H activation of 2-(arylazo)phenols. Synthesis, structure, and spectral and electrochemical properties of some organoiridium complexes

Reaction of 2-(2′,6′-dimethylphenylazo)-4-methylphenol with [Ir(PPh3)3Cl] in refluxing ethanol in the presence of a base (NEt3) affords an organoiridium complex 5, where the 2-(2′,6′-dimethylphenylazo)-4-methylphenol is coordinated to iridium, via C–H activation of a methyl group, as a dianionic tridentate C,N,O-donor. Two triphenylphosphines and a hydride are also coordinated to the metal center. A similar reaction carried out in toluene affords complex 5 along with a similar complex 7, where a chloride is coordinated to iridium instead of the hydride. Reaction of 2-(2′-methylphenylazo)-4-methylphenol with [Ir(PPh3)3Cl] in refluxing ethanol in the presence of a base (NEt3) affords an organoiridium complex 12, where the 2-(2′-methylphenylazo)-4-methylphenol is coordinated to iridium, via C–H activation at the ortho position of the phenyl group in the 2′-methylphenylazo fragment, as a dianionic tridentate C,N,O-donor. Two triphenylphosphines and a hydride are also coordinated to the metal center. A similar reaction carried out in toluene affords a complex 12 along with a similar complex 13, where a chloride is coordinated to iridium instead of the hydride. Structures of complexes 5, 12 and 13 have been determined by X-ray crystallography. In all these complexes, the two triphenylphosphines are trans. All these complexes show intense MLCT transitions in the visible region. Cyclic voltammetry on all the complexes shows an Ir(III)–Ir(IV) oxidation within 0.60–0.73 V vs. SCE, followed by an oxidation of the coordinated 2-(arylazo)phenolate ligand within 1.08–1.39 V vs. SCE. A reduction of the coordinated 2-(arylazo)phenolate ligand is observed within −1.10 to −1.26 V vs. SCE.

2-(2′,6′-Dimethylphenylazo)-4-methylphenol undergoes C–H activation of a methyl group in the arylazo fragment upon its reaction with [Ir(PPh3)3Cl] and affords an organoiridium complex 1, where the above ligand is coordinated as a tridentate C,N,O-donor. Similar reaction of 2-(2′-methylphenylazo)-4-methylphenol affords complex 2 via phenyl C–H activation.Figure optionsDownload as PowerPoint slide