We report that a bismuth–palladium pincer complex (BiPdCl) catalyzes the aldol-type coupling of aldehydes and methyl isocyanoacetate with unusually rapid turnover at ambient conditions, providing a platform to interrogate how heavy main-group ligands modulate catalytic energy landscapes. Kinetic and stoichiometric studies reveal saturation behavior toward both substrates and a palladium–isocyanoacetate adduct as the resting state under catalytic conditions. Systematic counterion and metal comparisons establish chloride as uniquely enabling and show that replacement of palladium with nickel leads to markedly diminished activity. Density functional theory calculations, supported by microkinetic modeling, rule out isonitrile-induced chloride migration from palladium to bismuth and instead support a productive pathway in which chloride-assisted enolate formation, concerted C–C/C–O bond formation, and subsequent release of an N,O-carbene, with carbene tautomerization to the oxazoline product constituting the overall rate-limiting event. Computational comparison with representative palladium catalysts lacking a bismuthinide ligand further reveals that the bismuth fragment plays a critical role in selectively modulating the catalytic energy landscape by preventing thermodynamic trapping. Together, these results establish a mechanistically grounded design principle in which synergistic heavy-pnictogen ligation and anion coordination can be used to suppress thermodynamic trapping and enable efficient transition-metal-catalyzed C–C bond formation.
Hu et al. (2026) studied this question.