Ligand-Induced Reductive Elimination of Ethane from Azopyridine Palladium Dimethyl Complexes

Abstract

Reductive elimination (RE) is a critical step in many catalytic processes. The reductive elimination of unsaturated groups (aryl, vinyl and ethynyl) from Pd(II) species is considerably faster than RE of saturated alkyl groups. Pd(II) dimethyl complexes ligated by chelating diimine ligands are stable toward RE unless subjected to a thermal or redox stimulus. Herein, we report the spontaneous RE of ethane from (azpy)PdMe complexes and the unique role of the redox-active azopyridine (azpy) ligands in facilitating this reaction. The (azpy)PdMe complexes are air- and moisture-stable in the solid form, but they readily produce ethane upon dissolution in polar solvents at temperatures from 10 °C to room temperature without the need for an external oxidant or elevated temperatures. Experimental and computational studies indicate that a bimolecular methyl transfer precedes the reductive elimination step, where both steps are facilitated by the redox-active azopyridine ligand.

Autonomous Reaction Network Exploration in Homogeneous and Heterogeneous Catalysis

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Heavy atom oriented orbital angular momentum manipulation in metal-free organic phosphors

“…RAS-SF has been shown to accurately treat a variety of challenging electronic structure problems, including polyradicals, singlet ssion mechanisms, and charge transfer processes. [57][58][59][60][61] Recent work has enabled RAS-SF to predict accurate SOC elements, making it particularly useful to complement the HAAM design concept. Furthermore and vital to instantiating the HAAM strategy, RAS-SF can produce natural transition orbitals (NTO) that couple pairs of spin states, revealing the specic changes in electronic structure that give rise to spin-orbit interactions.…”

Heavy Atom Oriented Orbital Angular Momentum Manipulation in Metal-Free Organic Phosphors

“…RAS-SF has been shown to accurately treat a variety of challenging electronic structure problems, including polyradicals, singlet fission mechanisms, and charge transfer processes. [43][44][45][46][47] Recent work has enabled RAS-SF to predict accurate SOC elements, making it particularly useful to complement the HAAM design concept. Furthermore and vital to instantiating the HAAM strategy, RAS-SF can produce natural transition orbitals (NTO) that couple pairs of spin states, revealing the specific changes in electronic structure that give rise to spin-orbit interactions.…”