A NiII-bis(diphosphine)-hydride complex containing proton relays - Structural characterization and electrocatalytic studies

Parthapratim Das, Ryan M. Stolley, Edwin F. Van Der Eide, Monte Helm

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

The synthesis of the 1,5-diphenyl-3,7-diisopropyl-1,5-diaza-3,7-diphosphacyclooctane ligand, PiPr2NPh2, is reported. Two equivalents of the ligand react with [Ni(CH3CN)6](BF4)2 to form the bis(diphosphine)-NiII complex [Ni(PiPr2NPh2)2](BF4)2, which acts as a proton reduction electrocatalyst. In addition to [Ni(PiPr2NPh2)2]2+, we report the synthesis and structural characterization of the Ni0 complex Ni(PiPr2NPh2)2 and the NiII-hydride complex [HNi(PiPr2NPh2)2]BF4. The [HNi(PiPr2NPh2)2]BF4 complex represents the first NiII-hydride in the [Ni(PR2NR2)2]2+ family of compounds to be structurally characterized. In addition to the experimental data, the mechanism of electrocatalysis facilitated by [Ni(PiPr2NPh2)2]2+ is analyzed by using linear free energy relationships recently established for the [Ni(PR2NR2)2]2+ family.

Original languageEnglish
Pages (from-to)4611-4618
Number of pages8
JournalEuropean Journal of Inorganic Chemistry
Volume2014
Issue number27
DOIs
Publication statusPublished - Sep 1 2014

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Hydrides
Protons
Ligands
Electrocatalysis
Electrocatalysts
Free energy
diphenyl
1,5-diaza-3,7-diphosphacyclooctane

Keywords

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

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

A NiII-bis(diphosphine)-hydride complex containing proton relays - Structural characterization and electrocatalytic studies. / Das, Parthapratim; Stolley, Ryan M.; Van Der Eide, Edwin F.; Helm, Monte.

In: European Journal of Inorganic Chemistry, Vol. 2014, No. 27, 01.09.2014, p. 4611-4618.

Research output: Contribution to journalArticle

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AB - The synthesis of the 1,5-diphenyl-3,7-diisopropyl-1,5-diaza-3,7-diphosphacyclooctane ligand, PiPr2NPh2, is reported. Two equivalents of the ligand react with [Ni(CH3CN)6](BF4)2 to form the bis(diphosphine)-NiII complex [Ni(PiPr2NPh2)2](BF4)2, which acts as a proton reduction electrocatalyst. In addition to [Ni(PiPr2NPh2)2]2+, we report the synthesis and structural characterization of the Ni0 complex Ni(PiPr2NPh2)2 and the NiII-hydride complex [HNi(PiPr2NPh2)2]BF4. The [HNi(PiPr2NPh2)2]BF4 complex represents the first NiII-hydride in the [Ni(PR2NR2)2]2+ family of compounds to be structurally characterized. In addition to the experimental data, the mechanism of electrocatalysis facilitated by [Ni(PiPr2NPh2)2]2+ is analyzed by using linear free energy relationships recently established for the [Ni(PR2NR2)2]2+ family.

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