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Abstract

Gas-phase ion trap mass spectrometry experiments and density functional theory calculations have been used to examine the routes to the formation of the 1,8-naphthyridine (napy) ligated geminally dimetallated phenyl complexes [(napy)Cu2(Ph)]+, [(napy)Ag2(Ph)]+ and [(napy)CuAg(Ph)]+ via extrusion of CO2 or SO2 under collision-induced dissociation conditions from their corresponding precursor complexes [(napy)Cu2(O2CPh)]+, [(napy)Ag2(O2CPh)]+, [(napy)CuAg(O2CPh)]+ and [(napy)Cu2(O2SPh)]+, [(napy)Ag2(O2SPh)]+, [(napy)CuAg(O2SPh)]+. Desulfination was found to be more facile than decarboxylation. Density functional theory calculations reveal that extrusion proceeds via two transition states: TS1 enables isomerization of the O,O-bridged benzoate to its O-bound form; TS2 involves extrusion of CO2 or SO2 with the concomitant formation of the organometallic cation and has the highest barrier. Of all the organometallic cations, only [(napy)Cu2(Ph)]+ reacts with water via hydrolysis to give [(napy)Cu2(OH)]+, consistent with density functional theory calculations which show that hydrolysis proceeds via the initial formation of the adduct [(napy)Cu2(Ph)(H2O)]+ which then proceeds via TS3 in which the coordinated H2O is deprotonated by the coordinated phenyl anion to give the product complex [(napy)Cu2(OH)(C6H6)]+, which then loses benzene.

Item Type:	Article
Authors/Creators:	Jin, Q and Li, J and Ariafard, A and Canty, AJ and O'Hair, RAJ
Keywords:	metal carboxylates, decarboxylation, metal sulfinates, desulfination, organocopper and organosilver, gas phase, mass spectrometry, density functional theory calculations
Journal or Publication Title:	European Journal of Mass Spectrometry
Publisher:	Im Publications
ISSN:	1469-0667
DOI / ID Number:	https://doi.org/10.1177/1469066718795959
Copyright Information:	Copyright The Author(s) 2018
Related URLs:	UTAS Profile: Canty, AJ
Item Statistics:	View statistics for this item

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