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 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.

Metadata

Item Type:	Article
Authors/Creators:	Portius, P. https://orcid.org/0000-0001-8133-8860 Bühl, M. George, M.W. Grevels, F.-W. Turner, J.J.
Copyright, Publisher and Additional Information:	© 2019 American Chemical Society. This is an author-produced version of a paper subsequently published in Organometallics. Uploaded in accordance with the publisher's self-archiving policy.
Keywords:	metal carbonyls; Berry pseudorotation; supercritical xenon; infrared spectroscopy
Dates:	Published: 11 November 2019 Published (online): 17 October 2019 Accepted: 1 October 2019
Institution:	The University of Sheffield
Academic Units:	The University of Sheffield > Faculty of Science (Sheffield) > Department of Chemistry (Sheffield)
Depositing User:	Symplectic Sheffield
Date Deposited:	16 Oct 2019 11:34
Last Modified:	16 Dec 2021 13:39
Status:	Published
Publisher:	American Chemical Society
Refereed:	Yes
Identification Number:	10.1021/acs.organomet.9b00559
Open Archives Initiative ID (OAI ID):	oai:eprints.whiterose.ac.uk:152140

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Structure and dynamics of iron pentacarbonyl

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