Theoretical analysis of mechanistic pathways for hydrogen evolution catalyzed by cobaloximes

Brian H. Solis, Sharon Hammes-Schiffer

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The mechanistic pathways for hydrogen evolution catalyzed by cobalt complexes with supporting diglyoxime ligands are analyzed with computational methods. The cobaloximes studied are Co(dmgBF2)2 (dmg = dimethylglyoxime) and Co(dpgBF2)2 (dpg = diphenylglyoxime) in acetonitrile. The reduction potentials and pKa values are calculated with density functional theory in conjunction with isodesmic reactions, incorporating the possibility of axial solvent ligand loss during the reduction process. The solvent reorganization energies for electron transfer between the cobalt complex and a metal electrode and the inner-sphere reorganization energies accounting for intramolecular rearrangements and the possibility of ligand loss are also calculated. The relative reduction potentials agree quantitatively with the available experimental values. The pKas and reorganization energies agree qualitatively with estimates based on experimental data. The calculations suggest that a peak measured at ca.-1.0 V vs SCE in cyclic voltammetry experiments for Co(dmgBF 2)2 is more likely to correspond to the Co IIH/CoIH reduction potential than the Co IIIH/CoIIH reduction potential. The calculations also predict pKa values of Co-hydride complexes and reduction potentials for both cobaloximes that have not been determined experimentally. The results are consistent with a mechanism in which the Co(III) and Co(II) complexes have two axial solvent ligands and the Co(I) complex has a single axial ligand along the reaction pathway. Analysis of the free energy diagrams generated for six different monometallic and bimetallic hydrogen production pathways identified the most favorable pathways for Co(dmgBF2)2 and tosic acid. The thermodynamically favored monometallic pathway passes through a Co(III)H intermediate, and Co(II)H reacts with the acid to produce H 2. The thermodynamically favored bimetallic pathways also pass through the Co(III)H intermediate, but the pathways in which two Co(III)H or two Co(II)H complexes react to produce H2 are not thermodynamically distinguishable with these methods. On the basis of the electrostatic work term associated with bringing the two cobalt complexes together in solution, the preferred bimetallic pathway involves the reaction of two Co(III)H complexes to produce H2. This mechanistic insight is important for designing more effective catalysts for solar energy conversion.

Original languageEnglish (US)
Pages (from-to)11252-11262
Number of pages11
JournalInorganic Chemistry
Issue number21
StatePublished - Nov 7 2011
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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