title: Unimolecular dissociation of anions derived from maleic acid (MaH2) in the gas phase: MaH- and MaMgCl--- relationship to Grignard chemistry and reductive CO2 fixation.
abstract: We have conducted collision induced dissociation experiments on the hydrogen maleate anion (MaH(-), m/z = 115) and the anionic maleate MgCl complex (MaMgC(-), m/z = 173). In addition, we have computationally investigated the observed fragmentation reactions. We find that both anions readily undergo two consecutive decarboxylations resulting in product ions at m/z = 71 and 27 for MaH(-), and at m/z = 129 and 85 for MaMgCl(-). The first decarboxylation is more facile for MaMgCl(-) than for MaH(-), while loss of CO(2) from Ma(-CO(2))H(-) is more facile than for Ma(-CO(2))MgCl(-). We also find that MaH(-) loses water, and we propose a mechanism for this loss. No first-generation fragmentation product other than Ma(-CO(2))MgCl(-) is seen for MaMgCl(-). Based on the observed unimolecular chemistry, we discuss some of its implications on reductive CO(2)-fixation and Grignard chemistry.
authors: Mass Spectrometry Laboratory and Centre of Theoretical and Computational Chemistry, Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, N-0315 Oslo, Norway. g.b.miller@kjemi.uio.no.
authors: Glenn B S
authors: GB
authors: Miller
authors: Mass Spectrometry Laboratory and Centre of Theoretical and Computational Chemistry, Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, N-0315 Oslo, Norway. vincent.faeseke@unibas.ch.
authors: Vincent
authors: V
authors: Fäseke
authors: Mass Spectrometry Laboratory and Centre of Theoretical and Computational Chemistry, Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, N-0315 Oslo, Norway. einar.uggerud@kjemi.uio.no.
authors: Einar
authors: E
authors: Uggerud