Two new Ni(II) complexes, the homoleptic [Ni(8PCy 2NH)2]2+ complex (8PCy 2NH = 3,7-cyclohexyl-1-amino-3,7-diphosphacyclooctane) containing two pendant amines on adjacent ligands, and the heteroleptic [Ni(8PCy 2NH)(dppe)]2+ complex (dppe = bis(diphenylphosphino)ethane) containing only a single pendant amine, have been synthesized, and their electrochemical properties are reported. The [Ni(8PCy 2NH)(dppe)]2+ complex is capable of heterolytically cleaving hydrogen, allowing for the first observation of an endo-protonated nickel hydride related to the [Ni(PR 2NR′ 2)2]2+ family of complexes. The [Ni(8PCy 2NH)(dppe)]2+ complex did not exhibit electrocatalytic H2 oxidation activity; however, [Ni(8PCy 2NH)2]2+ is an active electrocatalyst for H2 oxidation with a maximum turnover frequency (kobs) of 18 s-1 under 1 atm H2 at Ecat/2 = -0.71 V versus the ferrocenium/ferrocene (Cp2Fe+/0) couple. In addition to an analysis of the effect of the number of pendant amines on the rates of electrocatalytic H2 oxidation of compounds related to the [Ni(PR 2NR′ 2)2]2+ family, the effect of the secondary pendant amine on intermolecular deprotonation is discussed.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry