Universität zu Köln

Harnying, Wacharee ORCID: 0000-0003-1538-4177, Wen, Hui-Chung ORCID: 0000-0003-2814-9942, Martens, Jonathan, Berden, Giel ORCID: 0000-0003-1500-922X, Oomens, Jos, Roithová, Jana ORCID: 0000-0001-5144-0688, Berkessel, Albrecht ORCID: 0000-0003-0470-7428, Schäfer, Mathias ORCID: 0000-0002-5943-4335 and Meijer, Anthony J. H. M. ORCID: 0000-0003-4803-3488 (2025). Gas-phase Curtius and Wolff rearrangement reactions investigated by tandem-MS, IR ion spectroscopy and theory. Physical Chemistry Chemical Physics, 27 (25). pp. 13543-13556. Royal Society of Chemistry. ISSN 1463-9076

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Abstract

The Curtius and the Wolff rearrangement reactions are investigated in the gas phase by tandem mass spectrometry (MS) and infrared ion spectroscopy (IRIS), probing the nature and intrinsic reactivity of three acyl azides and of one α-diazo keto analyte and that of their N 2 -loss products at temperatures around 300 K. Our study uses tailor-made precursor ions with innocent charge tags, which are activated upon collision-induced dissociation (CID). Our tandem-MS infrared ion spectroscopy (IRIS) study clearly evidences concerted N 2 -loss reactions delivering the ultimate reaction products of the Curtius reaction, i.e. , the isocyanates, and the ones of the Wolff reaction, i.e. , the ketenes. We show that this is fully consistent with the reaction mechanism predicted by quantum-chemical calculations. All IRIS data interpretation rests on computed linear IR spectra of ion structures identified by computational analysis based on DFT calculations with CCSD(T)-F12b energies.

Item Type:	Article
Creators:	Creators Email ORCID ORCID Put Code Harnying, Wacharee UNSPECIFIED https://orcid.org/0000-0003-1538-4177 UNSPECIFIED Wen, Hui-Chung UNSPECIFIED https://orcid.org/0000-0003-2814-9942 UNSPECIFIED Martens, Jonathan UNSPECIFIED UNSPECIFIED UNSPECIFIED Berden, Giel UNSPECIFIED https://orcid.org/0000-0003-1500-922X UNSPECIFIED Oomens, Jos UNSPECIFIED UNSPECIFIED UNSPECIFIED Roithová, Jana UNSPECIFIED https://orcid.org/0000-0001-5144-0688 UNSPECIFIED Berkessel, Albrecht UNSPECIFIED https://orcid.org/0000-0003-0470-7428 UNSPECIFIED Schäfer, Mathias UNSPECIFIED https://orcid.org/0000-0002-5943-4335 UNSPECIFIED Meijer, Anthony J. H. M. UNSPECIFIED https://orcid.org/0000-0003-4803-3488 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-811651
Identification Number:	10.1039/D5CP01532D
Journal or Publication Title:	Physical Chemistry Chemical Physics
Volume:	27
Number:	25
Page Range:	pp. 13543-13556
Number of Pages:	14
Date:	2025
Publisher:	Royal Society of Chemistry
ISSN:	1463-9076
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Organic Chemistry
Subjects:	Chemistry and allied sciences Life sciences
['eprint_fieldname_oa_funders' not defined]:	Publikationsfonds UzK
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/81165