Journal
CHEMSUSCHEM
Volume 10, Issue 22, Pages 4589-4598Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cssc.201701416
Keywords
cyclopentadienyl ligands; homogeneous catalysis; molecular electrochemistry; reaction mechanisms; water splitting
Funding
- State of Kansas from the University of Kansas New Faculty General Research Fund
- US National Science Foundation through the NSF REU Program in Chemistry at the University of Kansas [CHE-1560279]
- Center for Undergraduate Research at the University of Kansas
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1560279] Funding Source: National Science Foundation
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We demonstrate that [Cp*Rh] complexes bearing substituted 2,2'-bipyridyl ligands are effective hydrogen evolution catalysts (Cp*= eta(5)-pentamethylcyclopentadienyl). Disubstitution (at the 4 and 4' positions) of the bipyridyl ligand (namely -tBu, -H, and -CF3) modulates the catalytic overpotential, in part due to involvement of the reduced ligand character in formally rhodium(I) intermediates. These reduced species are synthesized and isolated here; protonation results in formation of complexes bearing the unusual eta(4)-pentamethylcyclopentadiene ligand, and the properties of these protonated intermediates further govern the catalytic performance. Electrochemical studies suggest that multiple mechanistic pathways are accessible, and that the operative pathway depends on the applied potential and solution conditions. Taken together, these results suggest synergy in metal-ligand cooperation that modulates the mechanisms of fuel-forming catalysis with organometallic compounds bearing multiple non-innocent ligands.
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