Year: 2022
Type: article
Abstract: Catalytic transformations involving Pd(0)/Pd(II) catalytic cycles are very well known, and processes involving high-valent Pd(III) and Pd(IV) and low-valent Pd(I) intermediates have also gained interest in recent years. Although low-valent Pd(I) intermediates are proposed in these catalytic cycles, isolated and characterized mononuclear Pd(I) species are very rare. Herein, we report the isolation of two heteroleptic mononuclear Pd(I) complexes stabilized by dithiapyridinophane ligands that were fully characterized by single-crystal X-ray diffraction; EPR, IR, UV–vis spectroscopies; and computational studies. Excitingly, one of these Pd(I) complexes shows Kumada Csp 3 –Csp 2 cross-coupling competency, and initial studies of the other shows direct evidence for Csp 3 –H bond activation proposed to occur at the Pd(I) center.
DOI: 10.1021/jacs.2c08765
Institution: University of Illinois Urbana-Champaign
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W4306721697