Journal of Physical Chemistry A, volume 120, issue 39, pages 7659-7670
Distinctive Coordination of CO vs N2 to Rhodium Cations: An Infrared and Computational Study
1
College
of Science and Mathematics, University of the Virgin Islands, St. Thomas, United States Virgin Islands 00802
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2
Department of Chemistry & Biochemistry, Kennesaw State University, Kennesaw, Georgia 30144, United States
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3
Department
of Chemistry, University of Georgia, Athens, Georgia 30602, United States
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Publication type: Journal Article
Publication date: 2016-09-23
Journal:
Journal of Physical Chemistry A
Quartile SCImago
Q2
Quartile WOS
Q2
Impact factor: 2.9
ISSN: 10895639, 15205215
Physical and Theoretical Chemistry
Abstract
Carbonyl and nitrogen complexes with Rh+ are produced in a molecular beam using laser ablation and a pulsed-nozzle source. Mass-selected ions of the form Rh(CO)n+ and Rh(N2)n+ are investigated via infrared laser photodissociation spectroscopy. The fragmentation patterns and infrared spectra provide information on the coordination and geometries of these complexes. The shifts in vibrational frequencies relative to the uncoordinated ligands give insight into the nature of the bonding interactions involved. Experimental band positions and intensities are compared to those predicted by density functional theory (DFT). Rh+ coordinates only four nitrogen molecules, whereas it can accommodate five carbonyl ligands. The fifth CO ligand resides in an axial site with bonding intermediate between coordination and solvation. The carbonyl stretch in Rh(CO)4+ (2160 cm-1) is blue-shifted with respect to the molecular CO vibration (2143 cm-1). Conversely, the N-N stretch in Rh(N2)4+ (2297 cm-1) is red-shifted with respect to the free N2 vibration (2330 cm-1). The opposite directions of these frequency shifts is explained by a combination of σ donation and electrostatic ligand polarization.
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Citations by publishers
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American Chemical Society (ACS)
9 publications, 30%
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1 publication, 3.33%
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1 publication, 3.33%
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- We do not take into account publications without a DOI.
- Statistics recalculated only for publications connected to researchers, organizations and labs registered on the platform.
- Statistics recalculated weekly.
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Brathwaite A. D., Abbott Lyon H., Duncan M. A. Distinctive Coordination of CO vs N2 to Rhodium Cations: An Infrared and Computational Study // Journal of Physical Chemistry A. 2016. Vol. 120. No. 39. pp. 7659-7670.
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Brathwaite A. D., Abbott Lyon H., Duncan M. A. Distinctive Coordination of CO vs N2 to Rhodium Cations: An Infrared and Computational Study // Journal of Physical Chemistry A. 2016. Vol. 120. No. 39. pp. 7659-7670.
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TY - JOUR
DO - 10.1021/acs.jpca.6b07749
UR - https://doi.org/10.1021/acs.jpca.6b07749
TI - Distinctive Coordination of CO vs N2 to Rhodium Cations: An Infrared and Computational Study
T2 - Journal of Physical Chemistry A
AU - Brathwaite, A D
AU - Abbott Lyon, Heather
AU - Duncan, Michael A.
PY - 2016
DA - 2016/09/23 00:00:00
PB - American Chemical Society (ACS)
SP - 7659-7670
IS - 39
VL - 120
SN - 1089-5639
SN - 1520-5215
ER -
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@article{2016_Brathwaite,
author = {A D Brathwaite and Heather Abbott Lyon and Michael A. Duncan},
title = {Distinctive Coordination of CO vs N2 to Rhodium Cations: An Infrared and Computational Study},
journal = {Journal of Physical Chemistry A},
year = {2016},
volume = {120},
publisher = {American Chemical Society (ACS)},
month = {sep},
url = {https://doi.org/10.1021/acs.jpca.6b07749},
number = {39},
pages = {7659--7670},
doi = {10.1021/acs.jpca.6b07749}
}
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MLA
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Brathwaite, A. D., et al. “Distinctive Coordination of CO vs N2 to Rhodium Cations: An Infrared and Computational Study.” Journal of Physical Chemistry A, vol. 120, no. 39, Sep. 2016, pp. 7659-7670. https://doi.org/10.1021/acs.jpca.6b07749.