Abstract
The synthesis, crystal structure and electrochemical properties of a Ni(II) Schiff base complex, [Ni(L)]PF6 (where L is 2,4,9,11,11-pentamethyl-2,3,4 triaza-1-one-4-amine) are reported herein. The complex has been characterized by its electrochemical behavior, X-ray crystallographic structural analysis, physio-chemical methods and spectroscopic techniques. Electrospray mass spectroscopic analysis gives a dominant ion peak with m/z = 296 which corresponds to the {[Ni(L)]PF6–HPF6}+ fragment. Cyclic voltammograms for [Ni(L)]PF6, obtained in DMF (0.1 M Bu4NPF6) at a glassy carbon electrode with a scan rate of 100 mV s−1, exhibit reversible ([NiII(L)]+/[NiI(L)]) reduction and chemically irreversible ([NiII(L)]+/[NiIII(L)]2+→ electroactive product) oxidation processes at −2.05 and 0.62 V, respectively. The diffusion coefficient, calculated using the Randles–Sevcik relationship, is 9.7 × 10−6 cm2 s−1. Electrochemical studies reveal that the NiI reduced form of the complex is capable of catalyzing CO2 reduction at a potential that is thermodynamically more favorable than for the reduced [Ni(N,N′-ethylenebis(acetylacetoneiminato)]complex. Spectroelectrochemical analyses following bulk electrolysis of [Ni(L)]PF6 under CO2 revealed the formation of oxalate and bicarbonate.
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Acknowledgments
The authors gratefully acknowledge financial assistance from the Australian Research Council and an Endeavour Award-2011 Post-doctoral Fellowship by DEEWR and AusAid of Australia to Dr. (Mrs.) M.Y.Udugala-Ganehenege of University of Peradeniya, Sri Lanka. Assistance given by Ms. S.S. Hettiarachchi and Ms. M.C.R Peiris in carrying out the bulk electrolysis and FTIR measurements also is highly appreciated.
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Udugala-Ganehenege, M.Y., Liu, Y., Forsyth, C. et al. Synthesis, characterization, crystal structure, electrochemical properties and electrocatalytic activity of an unexpected nickel(II) Schiff base complex derived from bis(acetylacetonato)nickel(II), acetone and ethylenediamine. Transition Met Chem 39, 883–891 (2014). https://doi.org/10.1007/s11243-014-9872-3
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DOI: https://doi.org/10.1007/s11243-014-9872-3