Transmetallation of alkyl and carboxylate ligands between Cp*(PMe3)Ir complexes and d8 Pt and Pd complexes is described.  Studies on the scope and kinetics of this reaction support a mechanism in which carboxylate dissociation from the Pt or Pd center precedes alkyl transfer from Ir.  Subsequent reaction of the resulting Pt or Pd alkyl complex enables functionalization of the hydrocarbyl ligands and suggests new opportunities for catalytic, non-directed C-C and C-H bond functionalization reactions. Based on this work, a Pd-catalyzed cross-coupling reaction between Cp*(PMe3)IrBn)2 and aryl halides was developed. Examining the scope of this reaction led to the discovery that Cp*(PMe3)IrMeCl promotes C-H activation of arene substrates that can undergo subsequent Pd-catalyzed cross-coupling with aryl iodides. This Ir-promoted, Pd-catalyzed direct arylation is notable for its meta- selectivity on substituted arenes lacking directing groups or a particular electronic bias.

Ir-promoted, Pd-catalyzed direct arylation of unactivated arenes

247th National Meeting (2014)

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