Towards Norcorrin: Hydrogenation Chemistry and the Heterodimerization of Nickel(II) Norcorrole

Liu, B.; Li, X.; Stępień, M.; Chmielewski, P. J.
Chem. Eur. J. 2015, 21, 7790-7797 | view at publisher's site

5,14-Dimesitylnorcorrolatonickel(II) was hydrogenated under mild conditions (room temperature, 1 atm H2, THF solution, 5 min.) in the presence of Raney nickel to yield nonaromatic derivatives that were isolated and characterized by NMR spectroscopy, UV/Vis spectrophotometry, HRMS, cyclic voltammetry, and X-ray diffraction analysis. The major hydrogenation product, 1,2,3,7,8,9-hexahydronorcorrolatonickel(II), underwent dimerization in the presence of p-chloranil to give a nonsymmetrically linked 2,3′-bis(norcorrole) system that can adopt eight different oxidation states over a redox potential window of 3 V and has a HOMO–LUMO gap of 0.92 V.