The reaction of cobaloximes with hydrogen: Products and thermodynamics

Estes, Deven P.; Grills, David C.; Norton, Jack R.

doi:10.1021/ja508200g

The reaction of cobaloximes with hydrogen: Products and thermodynamics

Journal Article · Wed Nov 26 00:00:00 EST 2014 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja508200g· OSTI ID:1183829

Estes, Deven P. ^[1]; Grills, David C. ^[2]; Norton, Jack R. ^[1]

Columbia Univ., New York, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

In this study, a cobalt hydride has been proposed as an intermediate in many reactions of the Co(dmgBF₂)₂L₂ system, but its observation has proven difficult. We have observed the UV–vis spectra of Co(dmgBF₂)₂L₂ (1) in CH₃CN under hydrogen pressures up to 70 atm. A Co(I) compound (6), with an exchangeable proton, is eventually formed. We have determined the bond dissociation free energy and pKa of the new O–H bond in 6 to be 50.5 kcal/mol and 13.4, respectively, in CH₃CN, matching previous reports.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

OSTI ID:: 1183829

Report Number(s):: BNL--107850-2015-JA; KC0304030

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 50 Vol. 136; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cobaloxime-Catalyzed Hydrogen Evolution in Photoredox-Facilitated Small-Molecule Functionalization: Cobaloxime-Catalyzed Hydrogen Evolution in Photoredox-Facilitated Small-Molecule Functionalization Cartwright, Kaitie C.; Davies, Alex M.; Tunge, Jon A. European Journal of Organic Chemistry, Vol. 2020, Issue 10 https://doi.org/10.1002/ejoc.201901170	journal	October 2019
Enhancing electrocatalytic hydrogen evolution by nickel salicylaldimine complexes with alkali metal cations in aqueous media Shao, Haiyan; Muduli, Subas K.; Tran, Phong D. Chemical Communications, Vol. 52, Issue 14 https://doi.org/10.1039/c5cc09456a	journal	January 2016
Evaluation of the coordination preferences and catalytic pathways of heteroaxial cobalt oximes towards hydrogen generation Basu, Debashis; Mazumder, Shivnath; Niklas, Jens Chemical Science, Vol. 7, Issue 5 https://doi.org/10.1039/c5sc04214c	journal	January 2016
Molecular engineered nanomaterials for catalytic hydrogen evolution and oxidation Coutard, Nathan; Kaeffer, Nicolas; Artero, Vincent Chemical Communications, Vol. 52, Issue 95 https://doi.org/10.1039/c6cc06311j	journal	January 2016
Cobaloxime-catalyzed hydration of terminal alkynes without acidic promoters Hou, Shengtai; Yang, Hongjian; Cheng, Bin Chemical Communications, Vol. 53, Issue 51 https://doi.org/10.1039/c7cc03919k	journal	January 2017
A highly site-selective radical sp ³ C–H amination of azaheterocycles Bentley, Keith W.; Dummit, Krysta A.; Van Humbeck, Jeffrey F. Chemical Science, Vol. 9, Issue 30 https://doi.org/10.1039/c8sc00590g	journal	January 2018
Reversible homolytic activation of water via metal–ligand cooperativity in a T-shaped Ni( ii ) complex Chang, Mu-Chieh; Jesse, Kate A.; Filatov, Alexander S. Chemical Science, Vol. 10, Issue 5 https://doi.org/10.1039/c8sc03719a	journal	January 2019
Coordination-induced weakening of ammonia, water, and hydrazine X–H bonds in a molybdenum complex Bezdek, Máté J.; Guo, Sheng; Chirik, Paul J. Science, Vol. 354, Issue 6313 https://doi.org/10.1126/science.aag0246	journal	November 2016

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