ABSTRACT
Novel nickel(ii) complexes bearing ( t butyl)bis(diphenylphosphanyl)amine and different halogenido ligands, [Ni(P,P)X2] = [Ni{ t BuN(PPh2)2-κ2P}X2], (X = Cl, Br, I) are prepared, characterized by IR and NMR spectroscopy, mass spectrometry and X-ray crystallography, and tested as catalysts in the Kumada cross-coupling reaction of model substituted iodobenzenes and p-tolylmagnesium bromide. The data obtained together with DFT calculations indicate that these new catalysts operate in the Ni(i)-Ni(iii) mode. The highest catalytic activity and selectivity are exhibited by [Ni(P,P)Cl2], which is most easily reduced by the used Grignard reagent to the Ni(i) state. This process is much more energy demanding in the case of the bromido and iodido complexes, causing the appearance of the induction period. [Ni(P,P)Cl2] is also very active in the cross-couplings of substrates with iodine atoms sterically shielded by ortho substituents. The data obtained are in good accordance with the described positive effect of the increased electron-releasing power of N-substituents R' on the overall catalytic performance of [Ni{R'N(PPh2)2-κ2P}X2] complexes.
ABSTRACT
We report the highly efficient catalytic activity of a transition metal selenide-based coordination complex, [Ni{(SePi Pr2 )2 N}2 ], (1) for oxygen evolution and hydrogen evolution reactions (OER and HER, respectively) in alkaline solution. Very low overpotentials of 200â mV and 310â mV were required to achieve 10â mA cm-2 for OER and HER, respectively. The overpotential for OER is one of the lowest that has been reported up to now, making this one of the best OER electrocatalysts. In addition, this molecular complex exhibits an exceptionally high mass activity (111.02â A g-1 ) and a much higher TOF value (0.26â s-1 ) at a overpotential of 300â mV. This bifunctional electrocatalyst enables water electrolysis in alkaline solutions at a cell voltage of 1.54â V.
