Nickel Bis-Diphosphine Complexes: Controlling the Binding and Heterolysis of H2

Ryan M. Stolley, Jonathan M. Darmon, Parthapratim Das, Monte Helm

Research output: Contribution to journalReview article

4 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)2965-2974
Number of pages10
JournalOrganometallics
Volume35
Issue number17
DOIs
Publication statusPublished - Sep 12 2016

Fingerprint

Nickel
Amines
amines
nickel
Oxidation
oxidation
Deprotonation
electrocatalysts
Electrocatalysts
Electrochemical properties
Hydrides
ethane
hydrides
Hydrogen
Ligands
ligands
hydrogen

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Nickel Bis-Diphosphine Complexes : Controlling the Binding and Heterolysis of H2. / Stolley, Ryan M.; Darmon, Jonathan M.; Das, Parthapratim; Helm, Monte.

In: Organometallics, Vol. 35, No. 17, 12.09.2016, p. 2965-2974.

Research output: Contribution to journalReview article

Stolley, Ryan M. ; Darmon, Jonathan M. ; Das, Parthapratim ; Helm, Monte. / Nickel Bis-Diphosphine Complexes : Controlling the Binding and Heterolysis of H2. In: Organometallics. 2016 ; Vol. 35, No. 17. pp. 2965-2974.
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AB - 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.

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