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Title: Bimetallic Cooperativity in Proton Reduction with an Amido-Bridged Cobalt Catalyst

Journal Article · · Chemistry - A European Journal
ORCiD logo [1];  [1];  [2];  [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Wayne State Univ., Detroit, MI (United States)
  2. Marquette Univ., Milwaukee, WI (United States)
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Abstract The bimetallic catalyst [Co II 2 (L 1 )(bpy) 2 ]ClO 4 ( 1 ), in which L 1 is an [NN′ 2 O 2 ] fused ligand, efficiently reduced H + to H 2 in CH 3 CN in the presence of 100 equiv of HOAc with a turnover number of 18 and a Faradaic efficiency of 94 % after 3 h of bulk electrolysis at −1.6 V (vs. Ag/AgCl). This observation allowed the proposal that this bimetallic cooperativity is associated with distance, angle, and orbital alignment of the two Co centers, as promoted by the unique Co−N amido −Co environment offered by L 1 . Experimental results revealed that the parent [Co II Co II ] complex undergoes two successive metal‐based 1 e − reductions to generate the catalytically active species [Co I Co I ], and DFT calculations suggested that addition of a proton to one Co I triggers a cooperative 1 e − transfer by each of these Co I centers. This 2 e − transfer is an alternative route to generate a more reactive [Co II (Co II −H − )] hydride, thus avoiding the Co III −H − required in monometallic species. This [Co II (Co II −H − )] species then accepts another H + to release H 2 .

Research Organization:
Wayne State Univ., Detroit, MI (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
SC0001907
OSTI ID:
1533140
Alternate ID(s):
OSTI ID: 1400840
Journal Information:
Chemistry - A European Journal, Vol. 23, Issue 39; ISSN 0947-6539
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 21 works
Citation information provided by
Web of Science

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Cited By (3)

A Smorgasbord of 17 Cobalt Complexes Active for Photocatalytic Hydrogen Evolution journal June 2018
Multielectron Redox Chemistry of Transition Metal Complexes Supported by a Non-Innocent N 3 P 2 Ligand: Synthesis, Characterization, and Catalytic Properties : Multielectron Redox Chemistry of Transition Metal Complexes Supported by a Non-Innocent N3P2 Ligand: Synthesis, Characterization, and Catalytic Proper journal September 2018
Influence of nitro substituents on the redox, electronic, and proton reduction catalytic behavior of phenolate-based [N 2 O 3 ]-type cobalt( iii ) complexes journal January 2019

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