Title

Investigation of resonantly selected Raman spectra of intermediates in organic pyrolysis reactions

Authors

Authors

H. Matsui; N. Kobko; J. J. Dannenberg; S. H. Jonas;R. Viswanathan

Comments

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Abbreviated Journal Title

J. Raman Spectrosc.

Keywords

NITROSOKETENE INTERMEDIATE; MELDRUMS ACID; NITRONES; EXCHANGE; DENSITY; Spectroscopy

Abstract

The usefulness of UV resonance Raman (UVRR) spectroscopy in determining intermediate configurations in pyrolysis reactions was examined. We investigated the conformations of the nitrosoketene, E- and Z-isomers, generated via the pyrolysis of isonitroso Meldrum's acid by their characteristic vibrational wavenumbers. In this system, UVRR with 355 nm excitation worked exceptionally well to enhance selectively the nitrosoketene peaks. The signal was virtually free from other intermediates interferences, which was a major problem in IR spectroscopy. While both E- and Z-nitrosoketene were found as the intermediates of the isonitroso Meldrum's acid pyrolysis by UVRR, we consider that the observation of two isomers is due to their interconversions at 150degreesC, based upon computational analysis. Therefore, spectroscopic information on a shorter time-scale is necessary to determine the intermediate configuration in pyrolysis reactions. This method will still be useful for monitoring reactions at low temperatures, which may not involve significant interconversions of isomers. Copyright (C) 2002 John Wiley Sons, Ltd.

Journal Title

Journal of Raman Spectroscopy

Volume

33

Issue/Number

6

Publication Date

1-1-2002

Document Type

Article

Language

English

First Page

443

Last Page

448

WOS Identifier

WOS:000176419400005

ISSN

0377-0486

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