URBANA – Researchers at the University of Illinois Urbana-Champaign have reported a breakthrough in nickel catalysis that harnesses a rare oxidation state of nickel that has proved challenging to control yet is highly valued for its potential to facilitate important chemical reactions.
The researchers, led by Liviu Mirica , a professor of chemistry at Illinois, explain in a recently published paper in Nature Catalysis how they have overcome a long-standing challenge in the field of nickel catalysis by developing a new method for synthesizing thermally stable Ni(I) compounds that opens new avenues for building complex molecules.
“We have developed shelf-stable Ni(I) compounds that could dramatically change the playing field of nickel catalysis. And that's why we have an international patent for it, and we're working with pharmaceutical companies and chemical vendors who want to license it,” Mirica said.
Nickel-catalyzed cross-coupling reactions are widely used to form carbon–carbon and carbon–heteroatom bonds, essential steps in producing pharmaceuticals, agrochemicals, and advanced materials. Traditionally, these reactions rely on two forms of nickel – Ni(0) or Ni(II) – as catalysts. Catalytically competent Ni(I) sources have remained elusive, but attractive.
“This form of nickel is highly desirable partly because it may open up new avenues of reactivity that have remained elusive with traditional sources of nickel,” said Sagnik Chakrabarti, co-author and former graduate student in the Mirica group who worked on the project with graduate students Jubyeong Chae and Katy A. Knecht.
Mirica said previous approaches by chemists have used specialized ligands that limit the generality of Ni(I) in a reaction the way one would use Ni(II) or Ni(0) sources. By tapping into the unique properties of organic compounds called isocyanides, the Mirica group has developed a simple system that gets the chemistry to work.
In their study, they demonstrated how the commercially available isocyanides function as simple supporting ligands, which connect to the nickel atom and form stable, powerful catalysts that can be used to snap molecular pieces together with exceptional speed and precision, opening an untapped chemical space for reaction discovery.
Their Ni(I) complexes are readily available, shelf-stable, easily prepared, and easily handled catalysts that are efficient for a wide variety of chemical reactions. This is unique because most Ni(I) complexes tend to be rather unstable, which has limited their use in catalytic settings.
“We were able to put Ni(I), ‘nickel one’, in a bottle so people can use it on a wider scale for various synthetic applications,” Mirica said.
In the study, the researchers demonstrate that these new catalysts work in several of the most important reactions used to make pharmaceuticals, electronics, advanced materials, and more. They report the synthesis, characterization, and catalytic activity of two classes of Ni(I) isocyanide complexes: coordinatively saturated homoleptic compounds and coordinatively unsaturated Ni(I)-halide compounds. One is slightly more reactive than the other.
Their complexes exhibit rapid ligand substitution and demonstrate exceptional performance in Kumada, Suzuki–Miyaura, and Buchwald–Hartwig cross-coupling reactions, according to the study, and notably, they exhibit chemo-selectivity, displaying their versatility.
According to Mirica and Chakrabarti this new class of catalysts could be a game changer in nickel catalysis. Chakrabarti said there could be new reactions that could be discovered by directly introducing Ni(I) into reactions.
“And in fact, in the paper, we do talk about a new class of reactions that we developed and that has not been achieved with Ni catalysts before,” he said. “It's just a snippet of reactivity, not like a full vignette in itself, but it still shows that by synthesizing something that's different from what's out there, we can maybe coax unique reactivity.”
The research team also found that a tiny amount goes a long way.
“The interesting thing that we found is that we can use very, very tiny amounts of the nickel catalyst, which is unusual in Ni catalysis, which typically needs higher amounts of the catalyst,” Mirica said.
The study also highlights the structural diversity of isocyanides and their potential as spectator ligands for reaction discovery. Their study showed that this chemistry is not limited to just the one class of isocyanide they used, the tert -butyl isocyanide, but it's broadly applicable to other classes of isocyanides as well.
“So, the generality in using a bunch of different isocyanides bodes well for the future development of this chemistry,” Chakrabarti said.
Future work in the Mirica group will explore the fundamental structure and bonding of these unusually stable compounds, their new reactivity, and the differences in reactivity between alkyl and aryl isocyanide-supported complexes, which, according to their study, exhibit divergent catalytic behavior.
This research was supported by a grant from the National Science Foundation. The paper can be accessed at DOI: 10.1038/s41929-025-01473-9 . Liviu Mirica can be reached at mirica@illinois.edu
Nature Catalysis
Catalytically competent nickel(I)–isocyanide compounds for cross-coupling reactions
14-Jan-2026
The University of Illinois has filed a provisional patent (US patent application no. PCT/US2025/044429, title ‘Dinuclear Nickel Complexes and Cross-Coupling Catalysis Precursors’, inventors L.M.M., S.C. and J.B.C., filing date 2 September 2025) for the use of dinuclear NiI–isocyanide compounds in cross-coupling catalytic applications. All other authors declare no competing interests.