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 (kOA= 1.3 × 104-2.4 × 105M-1s-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.
All Science Journal Classification (ASJC) codes
- General Chemistry
- Colloid and Surface Chemistry