The Electronic Properties of Ni(PNN) Pincer Complexes Modulate Activity in Catalytic Hydrodehalogenation Reactions

Authors

Denan Wang, Marquette UniversityFollow
James R. Gardinier, Marquette UniversityFollow

Document Type

Article

Language

eng

Publication Date

12-20-2020

Publisher

Wiley

Source Publication

European Journal of Inorganic Chemistry

Source ISSN

1434-1948

Abstract

Three chloronickel(II) complexes of PNN‐ pincer ligands with pyrazolyl and diphenylphosphino donors appended to different arms of diarylamido anchors were prepared and fully characterized. The three derivatives (1‐OMe, 1‐Me, 1‐CF₃) differ only by the identity of the para‐aryl substituent on the pyrazolyl arm with 1‐OMe being 310 mV easier to oxidize than 1‐CF₃. All three complexes are competent catalysts for hydrodehalogenation reactions of 1‐bromooctane and a variety of aryl halides in dimethylacetamide using NaBH₄ as both base and hydride source. Comparative studies using diverse substrates showed that catalytic activity correlates with electron donor properties; 1‐OMe was superior to the other two. Deuterium labeling studies verified NaBD₄ as the deuteride source and excluded solvent‐assisted radical pathways.

Comments

Accepted version. European Journal of Inorganic Chemistry, Vol. 2020, No. 47 (December 20, 2020): 4425-4434. DOI. © 2020 Wiley. Used with permission.

Recommended Citation

Wang, Denan and Gardinier, James R., "The Electronic Properties of Ni(PNN) Pincer Complexes Modulate Activity in Catalytic Hydrodehalogenation Reactions" (2020). Chemistry Faculty Research and Publications. 1012.
https://epublications.marquette.edu/chem_fac/1012