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• W2022180571 startingPage "4748" @default.
• W2022180571 abstract "Electrospray ionization can generate microsolvated multiply charged metal ions for various metals and ligands, allowing exploration of chemistry within such clusters. The finite size of these systems permits comparing experimental results with accurate calculations, creating a natural laboratory to research ion solvation. Mass spectrometry has provided much insight into the stability and dissociation of ligated metal cations. While solvated singly charged ions tend to shrink by ligand evaporation, solvated polycations below a certain size exhibit charge reduction and/or ligand fragmentation due to organometallic reactions. Here we investigate the acetone complexes of representative divalent metals (Ca, Mn, Co, Ni, and Cu), comparing the results of collision-induced dissociation with the predictions of density functional theory. As for other solvated dications, channels involving proton or electron transfer compete with ligand loss and become dominant for smaller complexes. The heterolytic C-C bond cleavage is common, like in DMSO and acetonitrile complexes. Of primary interest is the unanticipated neutral ethylene loss, found for all metals studied except Cu and particularly intense for Ca and Mn. We focus on understanding that process in the context of competing dissociation pathways, as a function of metal identity and number of ligands. According to first-principles modeling, ethylene elimination proceeds along a complex path involving two intermediates. These results suggest that chemistry in microsolvated multiply charged ions may still hold major surprises." @default.
• W2022180571 created "2016-06-24" @default.
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• W2022180571 date "2007-05-16" @default.
• W2022180571 modified "2023-10-18" @default.
• W2022180571 title "Chemistry in Acetone Complexes of Metal Dications: A Remarkable Ethylene Production Pathway" @default.
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• W2022180571 doi "https://doi.org/10.1021/jp068574z" @default.
• W2022180571 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/17503788" @default.
• W2022180571 hasPublicationYear "2007" @default.
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