Journal
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
Volume 109, Issue 38, Pages 15127-15131Publisher
NATL ACAD SCIENCES
DOI: 10.1073/pnas.1213442109
Keywords
catalysis; renewable fuel
Categories
Funding
- National Science Foundation Center for Chemical Innovation in Solar Fuels [CHE-0802907]
- Center for Chemical Innovation postdoctoral fellowship
- Chevron-Phillips
- National Science Foundation Chemistry Research Instrumentation and Facilities: Departmental Multi-User Instrumentation (CRIF:MU) award [CHE-0639094]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [0802907] Funding Source: National Science Foundation
Ask authors/readers for more resources
Several cobalt complexes catalyze the evolution of hydrogen from acidic solutions, both homogeneously and at electrodes. The detailed molecular mechanisms of these transformations remain unresolved, largely owing to the fact that key reactive intermediates have eluded detection. One method of stabilizing reactive intermediates involves minimizing the overall reaction free-energy change. Here, we report a new cobalt(I) complex that reacts with tosylic acid to evolve hydrogen with a driving force of just 30 meV/Co. Protonation of Co-I produces a transient Co-III-H complex that was characterized by nuclear magnetic resonance spectroscopy. The CoIII-H intermediate decays by second-order kinetics with an inverse dependence on acid concentration. Analysis of the kinetics suggests that CoIII-H produces hydrogen by two competing pathways: a slower homolytic route involving two Co-III-H species and a dominant heterolytic channel in which a highly reactive Co-II-H transient is generated by Co-I reduction of Co-III-H.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available