The Application of Pulse Radiolysis to the Study of Ni(I) Intermediates in Ni-Catalyzed Cross-Coupling Reactions

Here we report the use of pulse radiolysis and spectroelectrochemistry to generate low-valent nickel intermediates relevant to synthetically important Ni-catalyzed cross-coupling reactions and interrogate their reactivities toward comproportionation and oxidative addition processes. Pulse radiolysis...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2021-06, Vol.143 (25), p.9332-9337
Main Authors: Till, Nicholas A, Oh, Seokjoon, MacMillan, David W. C, Bird, Matthew J
Format: Article
Language:English
Subjects:
Cross coupling reaction
Dissociation
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
Oxidative addition
Reactivity
Redox reactions
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Summary:Here we report the use of pulse radiolysis and spectroelectrochemistry to generate low-valent nickel intermediates relevant to synthetically important Ni-catalyzed cross-coupling reactions and interrogate their reactivities toward comproportionation and oxidative addition processes. Pulse radiolysis provided a direct means to generate singly reduced [(dtbbpy)­NiBr], enabling the identification of a rapid Ni(0)/Ni­(II) comproportionation process taking place under synthetically relevant electrolysis conditions. This approach also permitted the direct measurement of Ni­(I) oxidative addition rates with electronically differentiated aryl iodide electrophiles (k OA = 1.3 × 104–2.4 × 105 M–1 s–1), an elementary organometallic step often proposed in nickel-catalyzed cross-coupling reactions. Together, these results hold implications for a number of Ni-catalyzed cross-coupling processes.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.1c04652