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Cobalt catalyzed hydrogen evolution and formic acid dehydrogenation

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. http://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)
Related URLs:
URLURL TypeDescription
https://www.acs.org/content/acs/en/meetings/spring-2014.htmlOrganizationConference Website
ORCID:
AuthorORCID
Winkler, Jay R.0000-0002-4453-9716
Additional Information:© 2014 American Chemical Society.
Record Number:CaltechAUTHORS:20140429-155014408
Persistent URL:http://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:15 Sep 2017 22:41

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