Olefin Hydroarylation Catalyzed by (pyridyl-indolate)Pt(II) Complexes: Catalytic Efficiencies and Mechanistic Aspects

A series of Pt(II) complexes of the type (N–N)PtPh(SR_2) (N–N = 2,2′-pyridyl-indolate) were prepared, and their performance as catalysts for the hydroarylation of olefins was assessed. Evidence that the catalysis is homogeneous and is Pt-mediated is provided by control experiments with added hindered base (2,6-di-tert-butyl-4-methylpyridine) and Hg(0). Two potential catalytic intermediates, (^tBuPyInd)PtPh(C_2H_4) and (^tBuPyInd)Pt(CH_2CH_2Ph)(C_2H_4), were synthesized, and their catalytic efficacy was explored. Additionally, decomposition and deactivation pathways, including styrene formation via β-hydride elimination and ligand reductive demetalation, were identified.