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Vibrational Couplings in Hydridocarbonyl Complexes: A 2D-IR Perspective


Fernandez-Teran, Ricardo; Ruf, Jeannette; Hamm, Peter (2020). Vibrational Couplings in Hydridocarbonyl Complexes: A 2D-IR Perspective. Inorganic Chemistry, 59(11):7721-7726.

Abstract

Hydridocarbonyl complexes, a class of industrially relevant catalysts, contain both the M–H and M–CO moieties. Here, using two-dimensional infrared spectroscopy, we examine the coupling of the typically weak M–H stretching mode and the intense M(C≡O) mode. By studying a series of Ir(I)- and Ir(III)-based hydridocarbonyl complexes, we show that the arrangement of the H and CO ligands in a trans configuration leads to strong vibrational coupling and mode delocalization. In contrast, a cis arrangement leads to no coupling, with the localized M–H mode having a much larger anharmonicity. These results highlight a promising strategy for enhancing the M–H vibration by intensity borrowing from the strong C≡O modes in a trans configuration, allowing for direct determination by infrared spectroscopy of both the oxidation (by frequency shifts) and the protonation state (via vibrational coupling) of the complex, in mechanistic studies of proton-coupled electron transfer reactions.

Abstract

Hydridocarbonyl complexes, a class of industrially relevant catalysts, contain both the M–H and M–CO moieties. Here, using two-dimensional infrared spectroscopy, we examine the coupling of the typically weak M–H stretching mode and the intense M(C≡O) mode. By studying a series of Ir(I)- and Ir(III)-based hydridocarbonyl complexes, we show that the arrangement of the H and CO ligands in a trans configuration leads to strong vibrational coupling and mode delocalization. In contrast, a cis arrangement leads to no coupling, with the localized M–H mode having a much larger anharmonicity. These results highlight a promising strategy for enhancing the M–H vibration by intensity borrowing from the strong C≡O modes in a trans configuration, allowing for direct determination by infrared spectroscopy of both the oxidation (by frequency shifts) and the protonation state (via vibrational coupling) of the complex, in mechanistic studies of proton-coupled electron transfer reactions.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > Physical and Theoretical Chemistry
Physical Sciences > Inorganic Chemistry
Uncontrolled Keywords:Physical and Theoretical Chemistry, Inorganic Chemistry
Language:English
Date:1 June 2020
Deposited On:02 Feb 2021 12:59
Last Modified:03 Feb 2021 21:02
Publisher:American Chemical Society (ACS)
ISSN:0020-1669
OA Status:Closed
Publisher DOI:https://doi.org/10.1021/acs.inorgchem.0c00750
PubMed ID:32410448

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Content: Accepted Version
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Size: 438kB
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Embargo till: 2021-05-15