Isolation and Catalytic Reactivity of Mononuclear Palladium(I) Complexes

22 August 2022, Version 3
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Palladium complexes are among the most commonly used transition metal catalysts for different organic transformations with wide applications in the chemical synthesis. Currently, catalytic transformations involving Pd(0)/Pd(II) catalytic cycles are very well-known, and processes involving Pd(II)/Pd(III)/Pd(IV) intermediates are also gaining interest in recent years due to the increasing relevance of high-valent Pd species. By contrast, isolated low-valent Pd(I) complexes, especially mononuclear Pd(I) species, are very rare. Herein, we report the isolation of two heteroleptic Pd(I) complexes stabilized by dithiapyridinophane ligands that were fully characterized by single-crystal X-ray diffraction, EPR, IR, and UV-Vis spectroscopies, and computational studies. Excitingly, these Pd(I) complexes are shown to be superior catalysts for the Csp2-Csp3 Kumada cross-coupling reaction vs. their Pd(0) or Pd(II) analogs.

Keywords

Palladium(I)
cross-coupling reactions
electron paramagnetic resonance (EPR)
pyridinophane ligands
phosphine ligands
C-H activation

Supplementary materials

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