Structural and spectroscopic characterisation of C4 oxygenates relevant to structure/activity relationships of the hydrogenation of α,β-unsaturated carbonyls

Parker, S. F., Silverwood, I. P., Hamilton, N. G. and Lennon, D. (2016) Structural and spectroscopic characterisation of C4 oxygenates relevant to structure/activity relationships of the hydrogenation of α,β-unsaturated carbonyls. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 153, pp. 289-397. (doi: 10.1016/j.saa.2015.08.034) (PMID:26318704)

Abstract

In the present work, we have investigated the conformational isomerism and calculated the vibrational spectra of the C4 oxygenates: 3-butyne-2-one, 3-butene-2-one, 2-butanone and 2-butanol using density functional theory. The calculations are validated by comparison to structural data where available and new, experimental inelastic neutron scattering and infrared spectra of the compounds. We find that for 3-butene-2-one and 2-butanol the spectra show clear evidence for the presence of conformational isomerism and this is supported by the calculations. Complete vibrational assignments for all four molecules are provided and this provides the essential information needed to generate structure/activity relationships for the sequential catalytic hydrogenation of 3-butyne-2-one to 2-butanol.

• Item Type: Articles
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Lennon, Professor David and Silverwood, Dr Ian
• Authors: Parker, S. F., Silverwood, I. P., Hamilton, N. G., and Lennon, D.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
• Publisher: Elsevier
• ISSN: 1386-1425
• ISSN (Online): 1873-3557
• Copyright Holders: Copyright © 2015 Elsevier Ltd.
• First Published: First published in Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 155:289-397
• Publisher Policy: Reproduced in accordance with the copyright policy of the publisher