Catalyst Deactivation of a Monoligated CyJohnPhos-Bound Nickel(0) Complex

Cross-coupling catalysts are prone to unproductive side reactivity, which can limit their practical use in synthetic chemistry. A detailed understanding of these pathways and the conditions that enable them is important for reaction optimization and rational catalyst design. In this work, we report...

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Published inOrganometallics Vol. 42; no. 24; pp. 3438 - 3441
Main Authors Newman-Stonebraker, Samuel H., Raab, T. Judah, Doyle, Abigail G.
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 25.12.2023
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Summary:Cross-coupling catalysts are prone to unproductive side reactivity, which can limit their practical use in synthetic chemistry. A detailed understanding of these pathways and the conditions that enable them is important for reaction optimization and rational catalyst design. In this work, we report the off-cycle reactivity of a monoligated, (2-biphenyl)­dicyclohexylphosphine (CyJohnPhos)-bound Ni0 complex following product-forming reductive elimination. In the absence of substrate, free phosphine ligand, or π-accepting additives, dimerization of (CyJohnPhos)­Ni0 occurs, followed by C–P bond activation of the ligand to form a phosphido-bridged Ni0/NiII dimer; both the Ni0/Ni0 and Ni0/NiII dimers were structurally characterized. Monomeric (CyJohnPhos)­Ni0 must be intercepted by the substrate or free ligand to prevent irreversible dimerization and catalyst deactivation.
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Present Addresses Department of Chemistry, Yale University, New Haven, CT 06511
S. H. N.-S. and T. J. R. contributed equally.
ISSN:0276-7333
1520-6041
DOI:10.1021/acs.organomet.3c00450