Gas-phase Curtius and Wolff rearrangement reactions investigated by tandem-MS, IR ion spectroscopy and theory†
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 N2-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 N2-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.