Sieh, Daniel and Lacy, David C. and Peters, Jonas C. and Kubiak, Clifford P. (2015) Reduction of CO₂ by Pyridine Monoimine Molybdenum Carbonyl Complexes: Cooperative Metal–Ligand Binding of CO₂. Chemistry: a European Journal, 21 (23). pp. 8497-8503. ISSN 0947-6539. PMCID PMC4523092. doi:10.1002/chem.201500463. https://resolver.caltech.edu/CaltechAUTHORS:20150504-095804337
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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 CO₂ resulted in the formation of a new product that is assigned as a ligand-bound carboxylate, [(^(iPr₂Ph)PMI)Mo(CO)_3(CO₂)]²⁻, by NMR spectroscopic methods. The CO₂ adduct [(^(iPr₂Ph)PMI)Mo(CO)_3(CO₂)]²⁻ could not be isolated and fully characterized. However, the C_C coupling between the CO₂ molecule and the PDI ligand was confirmed by X-ray crystallographic characterization of one of the decomposition products of [(^(iPr₂Ph)PMI)Mo(CO)_3(CO₂)])²⁻.
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Alternate Title: | Reduction of CO2 by Pyridine Monoimine Molybdenum Carbonyl Complexes: Cooperative Metal–Ligand Binding of CO2 | ||||||||||||
Additional Information: | © 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Received: February 4, 2015. Article first published online: 29 Apr. 2015. This material is based upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the US Department of Energy under Award Number DE-SC0004993. D.C.L. is supported by the National Institutes of Health (Award Number F32M106726). The authors thank Michael Takase and Lawrence M. Henling for help with the absorption correction of the X-ray data and David VanderVelde for helpful discussions concerning NMR spectroscopy. Jesse D. Froehlich, Charles W. Machan, and Matthew D. Sampson are thanked for the introduction to IR-SEC techniques. | ||||||||||||
Group: | JCAP | ||||||||||||
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Issue or Number: | 23 | ||||||||||||
PubMed Central ID: | PMC4523092 | ||||||||||||
DOI: | 10.1002/chem.201500463 | ||||||||||||
Record Number: | CaltechAUTHORS:20150504-095804337 | ||||||||||||
Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20150504-095804337 | ||||||||||||
Official Citation: | Sieh, D., Lacy, D. C., Peters, J. C. and Kubiak, C. P. (2015), Reduction of CO2 by Pyridine Monoimine Molybdenum Carbonyl Complexes: Cooperative Metal–Ligand Binding of CO2. Chem. Eur. J., 21: 8497–8503. doi: 10.1002/chem.201500463 | ||||||||||||
Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||||||||||
ID Code: | 57184 | ||||||||||||
Collection: | CaltechAUTHORS | ||||||||||||
Deposited By: | Tony Diaz | ||||||||||||
Deposited On: | 04 May 2015 17:10 | ||||||||||||
Last Modified: | 06 Jun 2022 19:26 |
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