Structure and Dynamics of Iron Pentacarbonyl

Peter Portius; Michael Bühl; Michael W. George; Friedrich Wilhelm Grevels; James J. Turner

doi:10.1021/acs.organomet.9b00559

Structure and Dynamics of Iron Pentacarbonyl

Peter Portius, Michael Bühl, Michael W. George, Friedrich Wilhelm Grevels, James J. Turner

Department of Chemical and Environmental Engineering

Research output: Journal Publication › Article › peer-review

23 Citations (Scopus)

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Abstract

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 E_a = 2.5 ± 0.4 kcal mol^-1 by quantitative analysis of the temperature-dependent spectral line shape. This compares well with the range of E_a/(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.

Original language	English
Pages (from-to)	4288-4297
Number of pages	10
Journal	Organometallics
Volume	38
Issue number	21
DOIs	https://doi.org/10.1021/acs.organomet.9b00559
Publication status	Published - 11 Nov 2019

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/acs.organomet.9b00559

Structure and dynamics of iron pentacarbonylAccepted author manuscript, 3.03 MBLicence: CC BY

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title = "Structure and Dynamics of Iron Pentacarbonyl",

abstract = "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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T1 - Structure and Dynamics of Iron Pentacarbonyl

AU - Portius, Peter

AU - Bühl, Michael

AU - George, Michael W.

AU - Grevels, Friedrich Wilhelm

AU - Turner, James J.

PY - 2019/11/11

Y1 - 2019/11/11

N2 - 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.

AB - 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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Structure and Dynamics of Iron Pentacarbonyl

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