Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published December 1, 2010 | Supplemental Material
Journal Article Open

Mechanism of H_2 Evolution from a Photogenerated Hydridocobaloxime

Abstract

Proton transfer from the triplet excited state of brominated naphthol to a difluoroboryl bridged Co^I-diglyoxime complex, forming Co^(III)H, was monitored via transient absorption. The second-order rate constant for Co^(III)H formation is in the range (3.5−4.7) × 10^9 M^(−1) s^(−1), with proton transfer coupled to excited-state deactivation of the photoacid. Co^(III)H is subsequently reduced by excess Co^I-diglyoxime in solution to produce Co^(II)H (k_(red) = 9.2 × 10^6 M^(−1) s^(−1)), which is then protonated to yield Co^(II)-diglyoxime and H_2.

Additional Information

© 2010 American Chemical Society. Received October 17, 2010. Publication Date (Web): November 10, 2010. We thank Bruce Brunschwig, Alec Durrell, Maraia Ener, Jonas Peters, and Jeff Warren for helpful discussions and experimental advice. Charles McCrory and Jacob Good are acknowledged for generous assistance with GC measurements. This work was supported by an NSF Center for Chemical Innovation (Powering the Planet, CHE-0947829), the Arnold and Mabel Beckman Foundation, and CCSER (Gordon and Betty Moore Foundation). J.L.D. was supported by an NSF Graduate Research Fellowship.

Attached Files

Supplemental Material - ja109351h_si_001.pdf

Files

ja109351h_si_001.pdf
Files (2.1 MB)
Name Size Download all
md5:39638f253a0a79e6cd06d127225fe8fe
2.1 MB Preview Download

Additional details

Created:
August 19, 2023
Modified:
October 21, 2023