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Titolo:
Probing the reactivity of oxomanganese-salen complexes: An electrospray tandem mass spectrometric study of highly reactive intermediates
Autore:
Feichtinger, D; Plattner, DA;
Indirizzi:
ETH Zurich, ETH Zentrum, Organ Chem Lab, CH-8092 Zurich, Switzerland ETH Zurich Zurich Switzerland CH-8092 m Lab, CH-8092 Zurich, Switzerland
Titolo Testata:
CHEMISTRY-A EUROPEAN JOURNAL
fascicolo: 3, volume: 7, anno: 2001,
pagine: 591 - 599
SICI:
0947-6539(20010202)7:3<591:PTROOC>2.0.ZU;2-X
Fonte:
ISI
Lingua:
ENG
Soggetto:
COLLISION-INDUCED DISSOCIATION; NITRIC-OXIDE SYNTHASE; C-H ACTIVATION; OXOCHROMIUM(V) CATIONS; THERMOCHEMICAL DETERMINATIONS; ASYMMETRIC EPOXIDATION; MOLECULAR-STRUCTURE; BINDING-ENERGIES; CARBON-MONOXIDE; KINETIC METHOD;
Keywords:
density functional calculations; epoxidations; gas-phase chemistry; manganese; mass spectrometry;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
82
Recensione:
Indirizzi per estratti:
Indirizzo: Plattner, DA ETH Zurich, ETH Zentrum, Organ Chem Lab, Univ Str 16, CH-8092Zurich, Switzerland ETH Zurich Univ Str 16 Zurich Switzerland CH-8092 witzerland
Citazione:
D. Feichtinger e D.A. Plattner, "Probing the reactivity of oxomanganese-salen complexes: An electrospray tandem mass spectrometric study of highly reactive intermediates", CHEM-EUR J, 7(3), 2001, pp. 591-599

Abstract

Electrospray ionization in combination with tandem mass spectro metric techniques has been employed to study the formation of oxomanganese-salen complexes upon oxidation of [Mn-III(salen)](+) cations as well as the properties and reactions of the oxidized species in the gas phase. Two species couldbe characterized as the principal oxidation products: the oxomanganese(v) complex, [Mn=O(salen)](+), which is the actual oxygen-transfer agent in epoxidation reactions, and the dinuclear, mu -oxo bridged [L(salen)Mn-O-Mn-(salen)L](2+) with two terminal ligands L; the latter acts as a reservoir species. The effects of various substituents in the 5- and 5'-positions, respectively of the salen ligand on the reactivity of the epoxidation catalyst were determined quantitatively from CID (collision-induced dissociation) experiments and B3LYP density functional calculations. Accordingly, the effect of axial donor ligands on the reactivity of the epoxidation catalyst was studied. Electron-withdrawing substitutents on the salen ligand and additional axial ligands decrease the stability and thus enhance the reactivity of the Mn=O moiety, while electron-donating salen substituents have a strong stabilizing effect.

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Documento generato il 05/07/20 alle ore 06:46:41