Microwave spectrum and theoretical investigation of trifluoroacetic sulfuric anhydride

Huff, Anna

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https://hdl.handle.net/2142/100572 Copy

Description

Title

Microwave spectrum and theoretical investigation of trifluoroacetic sulfuric anhydride

Author(s)

Huff, Anna

Contributor(s)

• Leopold, Ken
• Smith, CJ
• Mackenzie, Becca

Issue Date

2018-06-20

Keyword(s)

Small molecules

Abstract

Trifluoroacetic sulfuric anhydride, CF3COOSO2OH, has been produced under supersonic jet conditions from the reaction of sulfur trioxide and trifluoroacetic acid. The rotational spectra for both the parent and deuterated isotopologues have been recorded, but were notably weaker than similar spectra obtained for other carboxylic sulfuric anhydrides. The spectra were readily fit to a Watson A-reduced Hamiltonian with no evidence of internal rotation. M06-2X/6-311++G(3df,3pd) calculations indicate that the formation of CF3COOSO2OH proceeds through a π2 + π2 + σ2 cycloaddition mechanism analogous to that previously established for other carboxylic sulfuric anhydrides. The barrier to formation for CF3COOSO2OH calculated at the CCSD(T)/CBS(D-T) level is slightly positive ( 0.7 kcal/mol), in contrast to the slightly negative value obtained for the formation of its acetic acid analog (acetic sulfuric anhydride). The possible role of internal rotation in the formation of both systems will be discussed.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

eng

Permalink

http://hdl.handle.net/2142/100572

DOI

10.15278/isms.2018.WH06

Copyright and License Information

Copyright 2018 Anna Huff

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