Marinescu, Smaranda C. and Laga, Stephanie M. and Sattler, Aaron and Gray, Harry B. and Winkler, Jay R. (2014) Cobalt catalyzed hydrogen evolution and formic acid dehydrogenation. In: 247th ACS National Meeting & Exposition, March 16-20, 2014, Dallas, TX. https://resolver.caltech.edu/CaltechAUTHORS:20140429-155014408
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Abstract
A Co^I-triphos complex (triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane) reacts at room temp. with ptoulenesulfonic acid monohydrate in acetonitrile to generate hydrogen (0.5 equiv) and Co^(II) with a driving force of just 30 meV/Co. Protonation of Co^I produces a transient Co^(III)-H complex that has been characterized by NMR spectroscopy. The Co^(III)-H intermediate decays by second-order kinetics with an inverse dependence on acid concn. Anal. of the kinetics suggests that Co^(III)-H produces hydrogen by a dominant heterolytic channel in which a highly reactive Co^(II)-H transient is generated by Co^I redn. of Co^(III)-H. The Co^I-triphos complex also reacts with excess formic acid to produce H_2 and CO_2. The mechanism of this transformation has been probed electrochem. and in studies of the gas evolution kinetics.
Item Type: | Conference or Workshop Item (Paper) | ||||||||
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Additional Information: | © 2014 American Chemical Society. | ||||||||
Record Number: | CaltechAUTHORS:20140429-155014408 | ||||||||
Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20140429-155014408 | ||||||||
Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||||||
ID Code: | 45329 | ||||||||
Collection: | CaltechAUTHORS | ||||||||
Deposited By: | Tony Diaz | ||||||||
Deposited On: | 29 Apr 2014 23:19 | ||||||||
Last Modified: | 09 Mar 2020 13:19 |
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