Structure and dynamics of iron pentacarbonyl

Peter Portius; Michael Buehl; Michael George; Friedrich-Wilhelm Grevels; James Turner

doi:10.1021/acs.organomet.9b00559

Structure and dynamics of iron pentacarbonyl

Peter Portius, Michael Buehl, Michael George, Friedrich-Wilhelm Grevels, James Turner

Research output: Contribution to journal › Article › peer-review

Abstract

The dynamics of CO ligand scrambling in Fe(CO)₅ has been investigated by linear infrared spectroscopy in supercritical xen-on solution. The activation barrier for the Berry pseudorotation in Fe(CO)5 was determined experimentally as 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 Ea / (kcal mol−1) = 2.0 to 2.3 calculated by various DFT methods, and a 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
Early online date	17 Oct 2019
DOIs	https://doi.org/10.1021/acs.organomet.9b00559
Publication status	Published - 11 Nov 2019

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Portius_2019_Organometallics_Structure_VoR
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Structure and dynamics of iron pentacarbonyl (dataset)
Buehl, M. (Creator), University of St Andrews, 2019
DOI: 10.17630/2b3d2f0e-7add-46e0-9b2e-db94fbbbc0e1
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abstract = "The dynamics of CO ligand scrambling in Fe(CO)5 has been investigated by linear infrared spectroscopy in supercritical xen-on solution. The activation barrier for the Berry pseudorotation in Fe(CO)5 was determined experimentally as 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 a 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.",

author = "Peter Portius and Michael Buehl and Michael George and Friedrich-Wilhelm Grevels and James Turner",

note = "This work was supported by the European Union through a Marie Curie IntraEuropean Fellowship (PP, FP6-502440).",

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doi = "10.1021/acs.organomet.9b00559",

language = "English",

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T1 - Structure and dynamics of iron pentacarbonyl

AU - Portius, Peter

AU - Buehl, Michael

AU - George, Michael

AU - Grevels, Friedrich-Wilhelm

AU - Turner, James

N1 - This work was supported by the European Union through a Marie Curie IntraEuropean Fellowship (PP, FP6-502440).

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 xen-on solution. The activation barrier for the Berry pseudorotation in Fe(CO)5 was determined experimentally as 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 a 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 xen-on solution. The activation barrier for the Berry pseudorotation in Fe(CO)5 was determined experimentally as 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 a 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.

U2 - 10.1021/acs.organomet.9b00559

DO - 10.1021/acs.organomet.9b00559

M3 - Article

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VL - 38

SP - 4288

EP - 4297

JO - Organometallics

JF - Organometallics

IS - 21

ER -

Structure and dynamics of iron pentacarbonyl

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Structure and dynamics of iron pentacarbonyl (dataset)

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