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

Journal Article · · Organometallics
 [1];  [1];  [1];  [1]
  1. Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
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In this work, two new Ni(II) complexes, the homoleptic [Ni(8PCy2NH)2]2+ complex (8PCy2NH = 3,7-cyclohexyl-1-amino-3,7-diphosphacyclooctane) containing two pendant amines on adjacent ligands, and the heteroleptic [Ni(8PCy2NH)(dppe)]2+ complex (dppe = bis(diphenylphosphino)ethane) containing only a single pendant amine, have been synthesized, and their electrochemical properties are reported. The [Ni(8PCy2NH)(dppe)]2+ complex is capable of heterolytically cleaving hydrogen, allowing for the first observation of an endo-protonated nickel hydride related to the [Ni(PR2NR'2)2]2+ family of complexes. The [Ni(8PCy2NH)(dppe)]2+ complex did not exhibit electrocatalytic H2 oxidation activity; however, [Ni(8PCy2NH)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(PR2NR'2)2]2+ family, the effect of the secondary pendant amine on intermolecular deprotonation is discussed.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
1388868
Journal Information:
Organometallics, Vol. 35, Issue 17; Related Information: CME partners with Pacific Northwest National Laboratory (lead); University of Illinois, Urbana-Champaign; Pennsylvania State University; University of Washington; University of Wyoming; ISSN 0276-7333
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science

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