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Generation and dissociation of oxygen- and chloride-bridged iron(III) and manganese(III) tetraphenylporphyrin dimer ions in the gas phase

✍ Scribed by Tuba Gozet; Lise Huynh; Diethard K. Bohme


Publisher
John Wiley and Sons
Year
2009
Tongue
English
Weight
229 KB
Volume
45
Category
Article
ISSN
1076-5174

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✦ Synopsis


Abstract

Electrospray ionization mass spectrometry (ESI/MS) has allowed the discovery of novel dimer ions emerging from solutions of metalloporphyrin salts and their investigation by collision‐induced dissociation (CID) with N~2~ molecules. ESI mass spectra have been recorded for the formation of the oxygen or chloride‐bridged dimer ions [(FeTPP)~2~OH]^+^, [(MnTPP)~2~OH]^+^, [(FeTPP)~2~Cl]^+^ and [(MnTPP)~2~Cl]^+^ derived from various solutions of FeTPPCl and MnTPPCl salts. The CID of [(FeTPP)~2~OH]^+^ proceeds mainly by neutral loss of (FeTPP)OH to form [FeTPP]^+^ and, to a minor extent, to form the charge‐reversed products. The CID of [(MnTPP)~2~OH]^+^ exhibits exclusively the product ion [MnTPP]^+^ by loss of neutral (MnTPP)OH. [(FeTPP)~2~Cl]^+^ and [(MnTPP)~2~Cl]^+^ dissociate by loss of (Fe/MnTPP)Cl to give rise to [Fe/MnTPP]^+^. [(FeTPP)~2~O]^+^ and [(FeTPP)~2~OH]^+^ were generated from a solution of the dimer, (FeTPP)~2~O. Dissociation of [(FeTPP)~2~O]^+^ yields two product ions, [FeTPP]^+^ and [(FeTPP)O]^+^, with higher onsets compared to the equivalent fragments formed from [(FeTPP)~2~OH]^+^. Copyright © 2009 John Wiley & Sons, Ltd.