Reactivity of a Nickel(II) Bis(amidate) Complex withmeta-Chloroperbenzoic Acid: Formation of a Potent Oxidizing Species

Article English OPEN
Corona, Teresa ; Pfaff, Florian F. ; Acuña-Parés, Ferran ; Draksharapu, Apparao ; Whiteoak, Christopher ; Martin-Diaconescu, Vlad ; Lloret-Fillol, Julio ; Browne, Wesley R. ; Ray, Kallol ; Company, Anna (2015)

Herein, we report the formation of a highly reactive nickel–oxygen species that has been trapped following reaction of a NiII precursor bearing a macrocyclic bis(amidate) ligand with meta-chloroperbenzoic acid (HmCPBA). This compound is only detectable at temperatures below 250 K and is much more reactive toward organic substrates (i.e., C[BOND]H bonds, C[DOUBLE BOND]C bonds, and sulfides) than previously reported well-defined nickel–oxygen species. Remarkably, this species is formed by heterolytic O[BOND]O bond cleavage of a Ni–HmCPBA precursor, which is concluded from experimental and computational data. On the basis of spectroscopy and DFT calculations, this reactive species is proposed to be a NiIII–oxyl compound.
  • References (18)
    18 references, page 1 of 2

    B. Ravel, M. Newville, Journal of Synchrotron Radiation 2005, 12, 537-541.

    J. J. Rehr, R. C. Albers, Reviews of Modern Physics 2000, 72, 621-654.

    Rypniewski, M. J. Maroney, S. Ciurli, Biochemical Journal 2012, 441, 1017-1026.

    Maroney, Journal of Biological Inorganic Chemistry 2012, 17, 353- 361.

    Musiani, M. J. Maroney, S. Ciurli, Journal of Biological Inorganic Chemistry 2014, 19, 319-334.

    Chivers, S. S. Pochapsky, T. C. Pochapsky, M. J. Maroney, Journal of the American Chemical Society 2010, 132, 10338- 10351.

    Cioslowski, D. J. Fox, Gaussian, Inc., Wallingford CT, 2009.

    A. D. Becke, J. Chem. Phys. 1993, 98, 1372-1377.

    A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5652.

    A. Schaefer, C. Huber, R. Ahlrichs, J. Chem. Phys. 1994, 100, 5829-5835.

  • Metrics
    views in OpenAIRE
    views in local repository
    downloads in local repository

    The information is available from the following content providers:

    From Number Of Views Number Of Downloads
    Sheffield Hallam University Research Archive - IRUS-UK 0 54
Share - Bookmark