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Distinctive unimolecular gas-phase reactivity of [M(en)2]2+ (M=Ni, Cu) dications and their inclusion complexes with the macrocyclic cavitand Cucurbit[8]uril
Authors:Tatyana Mitkina  Vladimir Fedin  Rosa Llusar  Ivan Sorribes  Cristian Vicent
Institution:A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, Novosibirsk, Russian Federation.
Abstract:Electrospray ionization mass spectrometry makes it possible to generate gas-phase bis-ethylenediamine nickel and copper dications, M(en)(2)](2+) (M = Ni, 1; M = Cu, 2), as well as their {M(en)(2)]@cuc8]}(2+) inclusion complexes with the macrocyclic cavitand cucurbit8]uril (cuc8]). The unimolecular gas-phase reactivity of these species has been investigated by electrospray ionization tandem mass spectrometry with a quadrupole-time-of-flight configuration. Distinctive fragmentation pathways have been observed for the free and encapsulated M(en)(2)](2+) (M = Ni, Cu) dications under collision-induced dissociation (CID) conditions. The dications M(en)(2)](2+) (M = Ni, Cu) dissociate according to several competitive pathways that involve intra-complex hydrogen or electron-transfer processes. Most of these channels are suppressed after encapsulation inside the cucurbit8]uril macrocycle and, as a consequence, a simplification of the {M(en)(2)]@cuc8]}(2+) fragmentation pattern is observed. The results obtained demonstrate that the encapsulation of a coordination complex inside a host molecule can be used to alter the nature of the product ions generated under CID conditions.
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