C-H activation of ethers by pyridine tethered PCsp3P-type iridium complexes

Iridium PCsp3P complexes featuring a novel bis(2-diphenylphosphinophenyl)-2-pyridylmethane ligand ((PCHP)-H-Py) are reported. C-H activation reactions between the dihydride complex [((PCP)-P-Py)Ir(H)(2)] and tetra-hydrofuran or methyl tert-butyl ether in the presence of a hydrogen acceptor, norbornene (NBE), at ambient temperature led exclusively to the hydrido oxyalkyl complexes, [((PCP)-P-Py)IrH(C4H7O)] and [((PCP)-P-Py) IrH((CH2OBu)-Bu-t)], respectively. The internal pyridine donor is important and stabilizes these species by coordination to the iridium center. The coordination of pyridine to the iridium center is labile, however, and its dissociation occurs in the presence of a suitable substrate, as demonstrated by the intramolecular nucleophilic attack of pyridine on a vinylidene intermediate generated from PhC equivalent to CH.