Visible Light Sensitized CO2 Activation by the Tetraaza [CoIIN4H(MeCN)]2+ Complex Investigated by FT-IR Spectroscopy and DFT Calculations
Abstract
In situ FT-IR measurements and electronic structure calculations are reported for the reduction of CO2 catalyzed by the macrocyclic complex [CoIIN4H]2+ (N4H = 2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(17),2,11,13,15-pentaene). Beginning from the [CoIIN4H]2+ resting state of the complex in wet acetonitrile solution, two different visible light sensitizers with substantially different reducing power are employed to access reduced states. Accessing reduced states of the complex with a [Ru(bpy)3]2+ sensitizer yields an infrared band at 1670 cm-1 attributed to carboxylate, which is also observed for an authentic sample of the one-electron reduced complex [CoN4H(MeCN)]+ in CO2 saturated acetonitrile solution. The results are interpreted based on calculations using the pure BP86 functional that correctly reproduces experimental geometries. Continuum solvation effects are also included. The calculations show that Co is reduced to CoIin the first reduction, which is consistent with experimental d-d spectra of square Co(I) macrocycle complexes. The energy of the CO2 adduct of the one-electron reduced catalyst complex is essentially the same as for [CoN4H(MeCN)]+, which implies that only a fraction of the latter forms an adduct with CO2. By contrast, the calculations indicate a crucial role for redox noninnocence of the macrocyclic ligand in the doubly reduced state, [CoI(N4H)-•], and show that [CoI(N4H)-•] binds partially reducedmore »
- Authors:
-
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- California Inst. of Technology (CalTech), Pasadena, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1511421
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 119; Journal Issue: 9; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Zhang, M., El-Roz, M., Frei, H., Mendoza-Cortes, J. L., Head-Gordon, M., Lacy, David C., and Peters, Jonas C. Visible Light Sensitized CO2 Activation by the Tetraaza [CoIIN4H(MeCN)]2+ Complex Investigated by FT-IR Spectroscopy and DFT Calculations. United States: N. p., 2015.
Web. doi:10.1021/jp5127738.
Zhang, M., El-Roz, M., Frei, H., Mendoza-Cortes, J. L., Head-Gordon, M., Lacy, David C., & Peters, Jonas C. Visible Light Sensitized CO2 Activation by the Tetraaza [CoIIN4H(MeCN)]2+ Complex Investigated by FT-IR Spectroscopy and DFT Calculations. United States. https://doi.org/10.1021/jp5127738
Zhang, M., El-Roz, M., Frei, H., Mendoza-Cortes, J. L., Head-Gordon, M., Lacy, David C., and Peters, Jonas C. Wed .
"Visible Light Sensitized CO2 Activation by the Tetraaza [CoIIN4H(MeCN)]2+ Complex Investigated by FT-IR Spectroscopy and DFT Calculations". United States. https://doi.org/10.1021/jp5127738. https://www.osti.gov/servlets/purl/1511421.
@article{osti_1511421,
title = {Visible Light Sensitized CO2 Activation by the Tetraaza [CoIIN4H(MeCN)]2+ Complex Investigated by FT-IR Spectroscopy and DFT Calculations},
author = {Zhang, M. and El-Roz, M. and Frei, H. and Mendoza-Cortes, J. L. and Head-Gordon, M. and Lacy, David C. and Peters, Jonas C.},
abstractNote = {In situ FT-IR measurements and electronic structure calculations are reported for the reduction of CO2 catalyzed by the macrocyclic complex [CoIIN4H]2+ (N4H = 2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(17),2,11,13,15-pentaene). Beginning from the [CoIIN4H]2+ resting state of the complex in wet acetonitrile solution, two different visible light sensitizers with substantially different reducing power are employed to access reduced states. Accessing reduced states of the complex with a [Ru(bpy)3]2+ sensitizer yields an infrared band at 1670 cm-1 attributed to carboxylate, which is also observed for an authentic sample of the one-electron reduced complex [CoN4H(MeCN)]+ in CO2 saturated acetonitrile solution. The results are interpreted based on calculations using the pure BP86 functional that correctly reproduces experimental geometries. Continuum solvation effects are also included. The calculations show that Co is reduced to CoIin the first reduction, which is consistent with experimental d-d spectra of square Co(I) macrocycle complexes. The energy of the CO2 adduct of the one-electron reduced catalyst complex is essentially the same as for [CoN4H(MeCN)]+, which implies that only a fraction of the latter forms an adduct with CO2. By contrast, the calculations indicate a crucial role for redox noninnocence of the macrocyclic ligand in the doubly reduced state, [CoI(N4H)-•], and show that [CoI(N4H)-•] binds partially reduced CO2 fairly strongly. Experimentally accessing [CoI(N4H)-•] with an Ir(bpy)3 sensitizer with greater reducing power closes the catalytic cycle as FT-IR spectroscopy shows CO production. Use of isotopically substituted C18O2 also shows clear evidence for 18O-substituted byproducts from CO2 reduction to CO.},
doi = {10.1021/jp5127738},
journal = {Journal of Physical Chemistry. C},
number = 9,
volume = 119,
place = {United States},
year = {Wed Feb 25 00:00:00 EST 2015},
month = {Wed Feb 25 00:00:00 EST 2015}
}
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