Structurally Diverse Bench-Stable Nickel(0) Pre-Catalysts: A Practical Toolkit for In Situ Ligation Protocols

11 February 2022, Version 1


A flurry of recent research has centered on harnessing the power of nickel catalysis in organic synthesis. These efforts have been bolstered by contemporaneous synthesis, characterization, and optimization of well-defined nickel (pre)catalysts with diverse structure and reactivity. In this report, we present the development of ten different bench-stable, 18-electron, formally zero-valent nickel–olefin complexes that are shown to be competent pre-catalysts in various reactions. Our investigation includes preparations of novel, bench stable Ni(COD)(L) complexes, in which L = quinone, cyclopentadienone, thiophene-S-oxide, and fulvene. Characterization by a battery of techniques, including NMR, IR, single-crystal X-ray diffraction, cyclic voltammetry, thermogravimetric analysis, and natural bond orbital analysis sheds light on the structure, bonding, and properties of these complexes. Kinetic profiling across a series of representative reactions reveals reactivity differences that stem from the nature of the ancillary ligand, underscoring the complementary relationships between each pre-catalyst within this toolkit.


ligand design

Supplementary materials

Supporting Info
Experimental procedures, characterization data for new compounds, copies of NMR spectra, X-ray crystallography data tables


Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.