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Electrocatalytic hydrogen evolution by macrocyclic cobalt and nickel complexes

Hu, Xile and Cossairt, Brandi M. and Brunschwig, Bruce B. and Lewis, Nathan S. and Peters, Jonas C. (2006) Electrocatalytic hydrogen evolution by macrocyclic cobalt and nickel complexes. Abstracts of Papers of the American Chemical Society, 231 . INOR 668. ISSN 0065-7727. https://resolver.caltech.edu/CaltechAUTHORS:20140729-143617509

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Abstract

A series of cobalt and nickel complexes with macrocyclic imine ligands such as difluoroboryldiglyxomime and [14]-Tetraene-N4 were synthesized for electrochem. hydrogen evolution catalysis. The complexes catalyzed the redn. of proton to dihydrogen at potentials as pos. as -0.26 V vs. SCE in acidic acetonitrile solns. The catalysis by the cobalt complexes was triggered by the redn. of cobalt(II) precursors to cobalt(I) species, while the catalysis by the nickel complexes was mediated by the redn. of nickel(II) precursors to nickel(II) stabilized ligand radicals. The influence of acid strengths on catalysis was discussed: for the cobalt mediated catalysis, using stronger acids as the proton sources gave higher catalytic rates; for the nickel mediated catalysis, the catalytic rates did not vary significantly when using different acids. Structure-function study of the catalysts was also described: more electron-deficient complexes catalyzed hydrogen evolution at more pos. potentials, yet with lower reaction rates.


Item Type:Article
ORCID:
AuthorORCID
Hu, Xile0000-0001-8335-1196
Cossairt, Brandi M.0000-0002-9891-3259
Brunschwig, Bruce B.0000-0002-6135-6727
Lewis, Nathan S.0000-0001-5245-0538
Peters, Jonas C.0000-0002-6610-4414
Additional Information:© 2006 American Chemical Society.
Record Number:CaltechAUTHORS:20140729-143617509
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20140729-143617509
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:47565
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:30 Jul 2014 18:45
Last Modified:07 Oct 2019 17:28

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