Reduction of CO 2 by Pyridine Monoimine Molybdenum Carbonyl Complexes: Cooperative Metal–Ligand Binding of CO 2
Abstract
Abstract [( Ar PMI)Mo(CO) 4 ] complexes (PMI=pyridine monoimine; Ar=Ph, 2,6‐di‐ iso ‐propylphenyl) were synthesized and their electrochemical properties were probed with cyclic voltammetry and infrared spectroelectrochemistry (IR‐SEC). The complexes undergo a reduction at more positive potentials than the related [(bipyridine)Mo(CO) 4 ] complex, which is ligand based according to IR‐SEC and DFT data. To probe the reaction product in more detail, stoichiometric chemical reduction and subsequent treatment with CO 2 resulted in the formation of a new product that is assigned as a ligand‐bound carboxylate, [( PMI)Mo(CO) 3 (CO 2 )] 2− , by NMR spectroscopic methods. The CO 2 adduct [( PMI)Mo(CO) 3 (CO 2 )] 2− could not be isolated and fully characterized. However, the CC coupling between the CO 2 molecule and the PDI ligand was confirmed by X‐ray crystallographic characterization of one of the decomposition products of [( PMI)Mo(CO) 3 (CO 2 )] 2− .
- Authors:
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1400917
- Grant/Contract Number:
- DE‐SC0004993
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- Chemistry - A European Journal
- Additional Journal Information:
- Journal Name: Chemistry - A European Journal Journal Volume: 21 Journal Issue: 23; Journal ID: ISSN 0947-6539
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Sieh, Daniel, Lacy, David C., Peters, Jonas C., and Kubiak, Clifford P. Reduction of CO 2 by Pyridine Monoimine Molybdenum Carbonyl Complexes: Cooperative Metal–Ligand Binding of CO 2. Germany: N. p., 2015.
Web. doi:10.1002/chem.201500463.
Sieh, Daniel, Lacy, David C., Peters, Jonas C., & Kubiak, Clifford P. Reduction of CO 2 by Pyridine Monoimine Molybdenum Carbonyl Complexes: Cooperative Metal–Ligand Binding of CO 2. Germany. https://doi.org/10.1002/chem.201500463
Sieh, Daniel, Lacy, David C., Peters, Jonas C., and Kubiak, Clifford P. Wed .
"Reduction of CO 2 by Pyridine Monoimine Molybdenum Carbonyl Complexes: Cooperative Metal–Ligand Binding of CO 2". Germany. https://doi.org/10.1002/chem.201500463.
@article{osti_1400917,
title = {Reduction of CO 2 by Pyridine Monoimine Molybdenum Carbonyl Complexes: Cooperative Metal–Ligand Binding of CO 2},
author = {Sieh, Daniel and Lacy, David C. and Peters, Jonas C. and Kubiak, Clifford P.},
abstractNote = {Abstract [( Ar PMI)Mo(CO) 4 ] complexes (PMI=pyridine monoimine; Ar=Ph, 2,6‐di‐ iso ‐propylphenyl) were synthesized and their electrochemical properties were probed with cyclic voltammetry and infrared spectroelectrochemistry (IR‐SEC). The complexes undergo a reduction at more positive potentials than the related [(bipyridine)Mo(CO) 4 ] complex, which is ligand based according to IR‐SEC and DFT data. To probe the reaction product in more detail, stoichiometric chemical reduction and subsequent treatment with CO 2 resulted in the formation of a new product that is assigned as a ligand‐bound carboxylate, [( PMI)Mo(CO) 3 (CO 2 )] 2− , by NMR spectroscopic methods. The CO 2 adduct [( PMI)Mo(CO) 3 (CO 2 )] 2− could not be isolated and fully characterized. However, the CC coupling between the CO 2 molecule and the PDI ligand was confirmed by X‐ray crystallographic characterization of one of the decomposition products of [( PMI)Mo(CO) 3 (CO 2 )] 2− .},
doi = {10.1002/chem.201500463},
journal = {Chemistry - A European Journal},
number = 23,
volume = 21,
place = {Germany},
year = {Wed Apr 29 00:00:00 EDT 2015},
month = {Wed Apr 29 00:00:00 EDT 2015}
}
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