Abstract
Catalysis by high-valent metals such as titanium(IV) impacts our lives daily through reactions like olefin polymerization. In any catalysis, optimization involves a careful choice of not just the metal but also the ancillary ligands. Because these choices dramatically impact the electronic structure of the system and, in turn, catalyst performance, new tools for catalyst development are needed. Understanding ancillary ligand effects is arguably one of the most critical aspects of catalyst optimization and, while parameters for phosphines have been used for decades with low-valent systems, a comparable system does not exist for high-valent metals. A new electronic parameter for ligand donation, derived from experiments on a high-valent chromium species, is now available. Here, we show that the new parameters enable quantitative determination of ancillary ligand effects on catalysis rate and, in some cases, even provide mechanistic information. Analysing reactions in this way can be used to design better catalyst architectures and paves the way for the use of such parameters in a host of high-valent processes.
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Acknowledgements
The authors acknowledge financial support from the US National Science Foundation under grant no. CHE-1562140. The authors thank R. Staples for assistance with X-ray crystallography.
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B.S.B. prepared and characterized all the chromium complexes, obtained the LDP values, carried out most of the X-ray diffraction studies used to obtain the %Vbur parameters, and modelled the rate data. T.J.M. synthesized the mono- and bi-dentate ligands, prepared and characterized all the titanium complexes, collected the rate data, and conducted the DOSY-NMR studies. A.L.O. conceived of the experiments and wrote the manuscript. All authors assisted in editing the manuscript and approved its contents.
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Billow, B., McDaniel, T. & Odom, A. Quantifying ligand effects in high-oxidation-state metal catalysis. Nature Chem 9, 837–842 (2017). https://doi.org/10.1038/nchem.2843
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DOI: https://doi.org/10.1038/nchem.2843