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The Ir(III) pyridylidene  (3) (Tp Me2 = \udhydrotris(3,5-dimethylpyrazolyl)borate) reacts with oxygen (air), under mild conditions, to afford a \udbicyclic ether-semiaminal species. The new structure derives formally from two oxidative events. One is \uddehydrogenative in nature (loss of 2 H) and the other consists in the insertion of an oxygen atom into a \udnon-activated benzylic C ―C bond. The reaction has been extended to a related iridacycle that contains a \udpyrazol co-ligand instead of the pyridylidene.    \udNowadays, there is increasing interest in the use of O 2 as aPeer reviewe

organometallics

Facile Oxygen Atom Insertion into Unactivated C(sp3)–C(sp2) Single Bonds in Reactions of Iridium(III) Complexes with O2