Reduction of CO₂ by Pyridine Monoimine Molybdenum Carbonyl Complexes: Cooperative Metal–Ligand Binding of CO₂
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⁻.
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.Attached Files
Accepted Version - nihms711222.pdf
Supplemental Material - chem_201500463_sm_miscellaneous_information.pdf
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Additional details
- Alternative title
- Reduction of CO2 by Pyridine Monoimine Molybdenum Carbonyl Complexes: Cooperative Metal–Ligand Binding of CO2
- PMCID
- PMC4523092
- Eprint ID
- 57184
- DOI
- 10.1002/chem.201500463
- Resolver ID
- CaltechAUTHORS:20150504-095804337
- Department of Energy (DOE)
- DE-SC0004993
- NIH
- F32M106726
- Created
-
2015-05-04Created from EPrint's datestamp field
- Updated
-
2022-06-06Created from EPrint's last_modified field
- Caltech groups
- JCAP