Hydrogen Atom Transfer by a High-Valent Nickel-Chloride Complex

J Am Chem Soc. 2018 Feb 7;140(5):1834-1841. doi: 10.1021/jacs.7b11953. Epub 2018 Jan 24.

Abstract

Oxo-metal-halide moieties have often been implicated as C-H bond activating oxidants with the terminal oxo-metal entity identified as the electrophilic oxidant. The electrophilic reactivity of metal-halide species has not been investigated. We have prepared a high-valent nickel-halide complex [NiIII(Cl)(L)] (2, L = N,N'-(2,6-dimethylphenyl)-2,6-pyridinedicarboxamide) by one-electron oxidation of a [NiII(Cl)(L)]- precursor. 2 was characterized using electronic absorption, electron paramagnetic resonance, and X-ray absorption spectroscopies and mass spectrometry. 2 reacted readily with substrates containing either phenolic O-H or hydrocarbon C-H bonds. Analysis of the Hammett, Evans-Polanyi, and Marcus relationships between the determined rate constants and substrate pKa, X-H bond dissociation energy, and oxidation potential, respectively, was performed. Through this analysis, we found that 2 reacted by a hydrogen atom transfer (HAT) mechanism. Our findings shine light on enzymatic high-valent oxo-metal-halide oxidants and open new avenues for oxidative halogenation catalyst design.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Catalysis
  • Chlorides / chemistry*
  • Hydrogen / chemistry*
  • Molecular Structure
  • Nickel / chemistry*
  • Organometallic Compounds / chemistry*

Substances

  • Chlorides
  • Organometallic Compounds
  • Nickel
  • Hydrogen