A Ni-II-Bis(diphosphine)-Hydride Complex Containing Proton Relays - Structural Characterization and Electrocatalytic Studies

作者：Das Parthapratim; Stolley Ryan M; van der Eide Edwin F; Helm Monte L^*

来源：European Journal of Inorganic Chemistry, 2014, 2014(27): 4611-4618.

DOI：10.1002/ejic.201402250

• Homogeneous catalysis
• Hydrogen
• Proton transport
• Nickel
• Diphosphine

The synthesis of the 1,5-diphenyl-3,7-diisopropyl-1,5-diaza3,7- diphosphacyclooctane ligand, (P2N2Ph)-N-iPr, is reported. Two equivalents of the ligand react with [Ni(CH3CN)(6)](BF4)(2) to form the bis(diphosphine)-Ni-II complex [Ni((P2N2Ph)-N-iPr)(2)]-(BF4)(2), which acts as a proton reduction electrocatalyst. In addition to [Ni((P2N2Ph)-N-iPr)(2)](2+), we report the synthesis and structural characterization of the Ni-0 complex Ni((P2N2Ph)-N-iPr)(2) and the Ni-II-hydride complex [HNi((P2N2Ph)-N-iPr)(2)]BF4. The [HNi((P2N2Ph)-N-iPr)(2)]BF4 complex represents the first Ni-II-hydride in the [Ni((P2N2R')-N-R)(2)](2+) family of compounds to be structurally characterized. In addition to the experimental data, the mechanism of electrocatalysis facilitated by [Ni-((P2N2Ph)-N-iPr)(2)](2+) is analyzed by using linear free energy relationships recently established for the [Ni((P2N2R')-N-R)(2)](2+) family.

• 出版日期2014-9