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Gas-phase studies of copper(I)-mediated CO2 extrusion followed by insertion of the heterocumulenes CS2 or phenylisocyanate

Yang, Y, Canty, AJ and O'Hair, RAJ 2020 , 'Gas-phase studies of copper(I)-mediated CO2 extrusion followed by insertion of the heterocumulenes CS2 or phenylisocyanate' , Journal of Mass Spectrometry, vol. 56, no. 4 , pp. 1-8 , doi: 10.1002/jms.4579.

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Abstract

The gas‐phase extrusion–insertion reactions of the copper complex [bathophenanthroline (Bphen)CuI(O2CC6H5)]2-, generated via electrospray ionization, was studied in a linear ion trap mass spectrometer with the combination of collision‐induced dissociation (CID) and ion‐molecule reaction (IMR) events. Multistage mass spectrometry (MSn) experiments and density functional theory (DFT) demonstrated that extrusion of carbon dioxide from [(Bphen)Cu(O2CC6H5)]2- (CID) gives the organometallic intermediate [(Bphen)Cu(C6H5)]2-, which subsequently reacts with carbon disulfide (IMR) via insertion to yield [(Bphen)Cu (SC(S)C6H5)]2−. The fragmentation of the product ion resulted in the formation of [Bphen]2−, [(Bphen)Cu]- and C6H5CS2− under CID conditions. The formation of the latter two charge separation products thus provides evidence of C–C bond formation in the IMR step. Although analogous studies with isocyanate, which is isoelectronic with CS2, showed a poor reactivity in the gas phase, the mechanistic understanding obtained from these model studies encourages future development of a solution phase protocol for the synthesis of amides from carboxylic acids and isocyanates mediated by copper(I) complexes.

Item Type: Article
Authors/Creators:Yang, Y and Canty, AJ and O'Hair, RAJ
Keywords: copper(I), cuprous, decarboxylation, carbon disulfide insertion, mass spectrometry, computation, DFT
Journal or Publication Title: Journal of Mass Spectrometry
Publisher: John Wiley & Sons Ltd
ISSN: 1076-5174
DOI / ID Number: 10.1002/jms.4579
Copyright Information:

Copyright 2020 John Wiley & Sons, Ltd.

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