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

Nicholas A. Till, Seokjoon Oh, David W.C. MacMillan, Matthew J. Bird

Research output: Contribution to journalArticlepeer-review

2 Scopus citations

Abstract

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.

Original languageEnglish (US)
Pages (from-to)9332-9337
Number of pages6
JournalJournal of the American Chemical Society
Volume143
Issue number25
DOIs
StatePublished - Jun 30 2021

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Fingerprint

Dive into the research topics of 'The Application of Pulse Radiolysis to the Study of Ni(I) Intermediates in Ni-Catalyzed Cross-Coupling Reactions'. Together they form a unique fingerprint.

Cite this