TY - JOUR
T1 - Isolation and Characterization of Heteroleptic Mononuclear Palladium(I) Complexes
AU - Tran, Giang N.
AU - Bouley, Bailey S.
AU - Mirica, Liviu M.
N1 - Funding Information:
This work was supported by the National Science Foundation (CHE-2102544 to L.M.M.). The authors thank Dr. Yung-Ching Wang for his help with recording the initial EPR spectra for these studies and Prof. Nigam P. Rath (Univ. of Missouri - St. Louis) for obtaining the crystal structures of Pd-1 , Pd-2 , Pd-3 , Pd-4 , and Pd-5 . The authors also thank all of the research facilities in the Department of Chemistry at the University of Illinois at Urbana-Champaign for their help.
Publisher Copyright:
© 2022 American Chemical Society.
PY - 2022/11/2
Y1 - 2022/11/2
N2 - 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 Csp3-Csp2 cross-coupling competency, and initial studies of the other shows direct evidence for Csp3-H bond activation proposed to occur at the Pd(I) center.
AB - 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 Csp3-Csp2 cross-coupling competency, and initial studies of the other shows direct evidence for Csp3-H bond activation proposed to occur at the Pd(I) center.
UR - http://www.scopus.com/inward/record.url?scp=85140642656&partnerID=8YFLogxK
U2 - 10.1021/jacs.2c08765
DO - 10.1021/jacs.2c08765
M3 - Article
C2 - 36257056
AN - SCOPUS:85140642656
SN - 0002-7863
VL - 144
SP - 20008
EP - 20015
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 43
ER -