The synthesis of NCOP pincer ligands ([1,3-C6H3(OPR2)(CH2NR2)]) and Iridium complexes of the type (NCOP)IrHCl is reported. When dehydrochlorinated by base, (NCOP)IrHCl reacts with acetophenone to give a product resulting from oxidative addition of the ortho-C-H bond and coordination of the acetophenone carbonyl oxygen, in analogy with the product formed from the reaction of (PCP)Ir precursos with acetophenone.1 In sharp contrast with the (PCP)Ir complexes, however, the (NCOP)Ir complex is found to catalyze the addition of the aryl ortho CH bond across alkene C-C double bonds. This is the first example of an iridium complex displaying catalytic activity of the type that has been pioneered by Murai and Chatani with ruthenium complexes,2 Given that the products of C-H addition /O-coordination to (PCP)Ir are coordinatively saturated, their inability to effect catalytic olefin insertion is not surprising. The catalitic activity displayed by the (NCOP)Ir products, in contrast, may be attributable to hemilability of the NCOP ligand.1. Zhang, X.; Kanzelberger, M.; Emge, T. J.; Goldman, A. S. 'Selective Addition to Iridium of Aryl C-H Bonds Ortho to Coordinationg Groups. Not Chelation-Assisted' J. Am. Chem. Soc. 2004 , 126, 13192 2. Murai, S.; Kakiuchi, F.; Sekine, S.; Tanaka, Y.; Kamatani, A.; Sonoda, M.; Chatani, N. 'Efficient Catalytic Addition of Aromatic Carbon-Hydrogen Bonds to Olefins'? Nature?, ?1993 ?, ?366?, 529

Selective addition of aryl CH bonds <i>ortho</i> to directing groups across olefin double bonds, catalyzed by new iridium complexes supported by phosphino-amino (NCOP) pincer ligands

245th National Meeting (2013)

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Selective addition of aryl CH bonds ortho to directing groups across olefin double bonds, catalyzed by new iridium complexes supported by phosphino-amino (NCOP) pincer ligands