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Gas‐phase chemistry of metal oxide anions: Reactions of dioxomanganate(III), MnO 2 − , and trioxomanganate(V), MnO 3 − , ions with monofluoro‐ and pentafluoro‐aromatic compounds
Author(s) -
Fokkens R. H.,
Gregor I. K.,
Nibbering N. M. M.
Publication year - 1992
Publication title -
organic mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0030-493X
DOI - 10.1002/oms.1210271010
Subject(s) - chemistry , fourier transform ion cyclotron resonance , nucleophile , ion , fluorine , proton affinity , metal , oxide , electron affinity (data page) , mass spectrometry , inorganic chemistry , gas phase , molecule , organic chemistry , catalysis , protonation , chromatography
Abstract Gas‐phase reactions of MnO 2 − and MnO 3 − ions with a series of monofluoro‐ and pentafluoro‐aromatic compounds, i.e. C 6 H 4 FX with X = o ‐, m ‐ and p ‐CHO and o ‐, m ‐ and p ‐OH and C 6 F 5 Y with Y = OH, OCH 3 , CHO, CN, NO 2 , COCH 3 and F, were studied at low pressures by Fourier transform ion cyclotron resonance mass spectrometry. The principal reaction channels identified involve electron transfer from the MnO 2 − and MnO 3 − ions to the fluorinated aromatic substrates and proton abstraction and nucleophilic displacement of fluorine by these oxometallate ions. The results obtained indicate that in the gas phase MnO 2 − is less basic than MnO 3 − and that neutral MnO 2 has a lower electron affinity than MnO 3 , both values lying between 0.52 and 0.94 eV.