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O2 activation by metal-ligand cooperation with Ir(I) PNP pincer complexes
Moran Feller1, Eyal Ben-Ari1, Yael Diskin-Posner1
1Departments of †Organic Chemistry and ‡Chemical Research Support, Weizmann Institute of Science, Rehovot 76100, Israel.
Abstract:
A unique mode of molecular oxygen activation, involving metal-ligand cooperation, is described. Ir pincer complexes [((t)BuPNP)Ir(R)] (R = C6H5 (1), CH2COCH3 (2)) react with O2 to form the dearomatized hydroxo complexes [((t)BuPNP*)Ir(R)(OH)] ((t)BuPNP* = deprotonated (t)BuPNP ligand), in a process which utilizes both O-atoms. Experimental evidence, including NMR, EPR, and mass analyses, indicates a binuclear mechanism involving an O-atom transfer by a peroxo intermediate.
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