Structure and dynamics of iron pentacarbonyl

The dynamics of CO ligand scrambling in Fe(CO)5 has been investigated by linear infrared spectroscopy in supercritical xenon solution. The activation barrier for the Berry pseudorotation in Fe(CO)5 was determined experimentally to be Ea = 2.5 ± 0.4 kcal mol–1 by quantitative analysis of the temperat...

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Main Authors: Portius, Peter, Bühl, Michael, George, Michael W., Grevels, Friedrich-Wilhelm, Turner, James J.
Format: Article
Language:English
Published: 2020
Subjects:
Online Access:https://eprints.nottingham.ac.uk/61358/
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author Portius, Peter
Bühl, Michael
George, Michael W.
Grevels, Friedrich-Wilhelm
Turner, James J.
author_facet Portius, Peter
Bühl, Michael
George, Michael W.
Grevels, Friedrich-Wilhelm
Turner, James J.
author_sort Portius, Peter
building Nottingham Research Data Repository
collection Online Access
description The dynamics of CO ligand scrambling in Fe(CO)5 has been investigated by linear infrared spectroscopy in supercritical xenon solution. The activation barrier for the Berry pseudorotation in Fe(CO)5 was determined experimentally to be Ea = 2.5 ± 0.4 kcal mol–1 by quantitative analysis of the temperature-dependent spectral line shape. This compares well with the range of Ea/(kcal mol–1) = 2.0 to 2.3 calculated by various DFT methods and the value of 1.6 ± 0.3 previously obtained from 2D IR measurements by Harris et al. ( Science 2008, 319, 1820). The involvement of Fe(CO)5···Xe interactions in the ligand scrambling process was tested computationally at the BP86-D3/AE2 level and found to be negligible.
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spelling nottingham-613582020-08-19T08:17:41Z https://eprints.nottingham.ac.uk/61358/ Structure and dynamics of iron pentacarbonyl Portius, Peter Bühl, Michael George, Michael W. Grevels, Friedrich-Wilhelm Turner, James J. The dynamics of CO ligand scrambling in Fe(CO)5 has been investigated by linear infrared spectroscopy in supercritical xenon solution. The activation barrier for the Berry pseudorotation in Fe(CO)5 was determined experimentally to be Ea = 2.5 ± 0.4 kcal mol–1 by quantitative analysis of the temperature-dependent spectral line shape. This compares well with the range of Ea/(kcal mol–1) = 2.0 to 2.3 calculated by various DFT methods and the value of 1.6 ± 0.3 previously obtained from 2D IR measurements by Harris et al. ( Science 2008, 319, 1820). The involvement of Fe(CO)5···Xe interactions in the ligand scrambling process was tested computationally at the BP86-D3/AE2 level and found to be negligible. 2020-11-11 Article PeerReviewed application/pdf en cc_by_nc https://eprints.nottingham.ac.uk/61358/1/ilovepdf_merged%20%2826%29.pdf Portius, Peter, Bühl, Michael, George, Michael W., Grevels, Friedrich-Wilhelm and Turner, James J. (2020) Structure and dynamics of iron pentacarbonyl. Organometallics, 38 (21). pp. 4288-4297. ISSN 0276-7333 Group theory; Plant derived food; Oscillation; Chemical structure; Infrared light http://dx.doi.org/10.1021/acs.organomet.9b00559 doi:10.1021/acs.organomet.9b00559 doi:10.1021/acs.organomet.9b00559
spellingShingle Group theory; Plant derived food; Oscillation; Chemical structure; Infrared light
Portius, Peter
Bühl, Michael
George, Michael W.
Grevels, Friedrich-Wilhelm
Turner, James J.
Structure and dynamics of iron pentacarbonyl
title Structure and dynamics of iron pentacarbonyl
title_full Structure and dynamics of iron pentacarbonyl
title_fullStr Structure and dynamics of iron pentacarbonyl
title_full_unstemmed Structure and dynamics of iron pentacarbonyl
title_short Structure and dynamics of iron pentacarbonyl
title_sort structure and dynamics of iron pentacarbonyl
topic Group theory; Plant derived food; Oscillation; Chemical structure; Infrared light
url https://eprints.nottingham.ac.uk/61358/
https://eprints.nottingham.ac.uk/61358/
https://eprints.nottingham.ac.uk/61358/