Well-Defined
Cobalt(I) Dihydrogen Catalyst: Experimental
Evidence for a Co(I)/Co(III) Redox Process in Olefin Hydrogenation
Version 3 2016-09-09, 16:02
Version 2 2016-09-08, 16:07
Version 1 2016-08-26, 21:29
Posted on 2016-08-29 - 00:00
The
synthesis of a cobalt dihydrogen CoI-(H2) complex
prepared from a CoI-(N2) precursor
supported by a monoanionic pincer bis(carbene) ligand, MesCCC (MesCCC = bis(mesityl-benzimidazol-2-ylidene)phenyl),
is described. This species is capable of H2/D2 scrambling and hydrogenating alkenes at room temperature. Stoichiometric
addition of HCl to the CoI-(N2) cleanly affords
the CoIII hydridochloride complex, which, upon the addition
of Cp2ZrHCl, evolves hydrogen gas and regenerates the CoI-(N2) complex. Furthermore, the catalytic olefin
hydrogenation activity of the CoI species was studied by
using multinuclear and parahydrogen (p-H2) induced polarization (PHIP) transfer NMR studies to elucidate catalytically
relevant intermediates, as well as to establish the role of the CoI-(H2) in the CoI/CoIII redox
cycle.
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Tokmic, Kenan; Markus, Charles R.; Zhu, Lingyang; Fout, Alison R. (2016). Well-Defined
Cobalt(I) Dihydrogen Catalyst: Experimental
Evidence for a Co(I)/Co(III) Redox Process in Olefin Hydrogenation. ACS Publications. Collection. https://doi.org/10.1021/jacs.6b07066
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AUTHORS (4)
KT
Kenan Tokmic
CM
Charles R. Markus
LZ
Lingyang Zhu
AF
Alison R. Fout