Generation and dissociation of oxygen‐ and chloride‐bridged iron(III) and manganese(III) tetraphenylporphyrin dimer ions in the gas phase |
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| Authors: | Tuba Gozet Lise Huynh Diethard K. Bohme |
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| Affiliation: | Department of Chemistry, Center for Research in Mass Spectrometry and Center for Research in Earth and Space Science, York University, Toronto, Ontario, M3J 1P3, Canada |
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| 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 N2 molecules. ESI mass spectra have been recorded for the formation of the oxygen or chloride‐bridged dimer ions [(FeTPP)2OH]+, [(MnTPP)2OH]+, [(FeTPP)2Cl]+ and [(MnTPP)2Cl]+ derived from various solutions of FeTPPCl and MnTPPCl salts. The CID of [(FeTPP)2OH]+ 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)2OH]+ exhibits exclusively the product ion [MnTPP]+ by loss of neutral (MnTPP)OH. [(FeTPP)2Cl]+ and [(MnTPP)2Cl]+ dissociate by loss of (Fe/MnTPP)Cl to give rise to [Fe/MnTPP]+. [(FeTPP)2O]+ and [(FeTPP)2OH]+ were generated from a solution of the dimer, (FeTPP)2O. Dissociation of [(FeTPP)2O]+ yields two product ions, [FeTPP]+ and [(FeTPP)O]+, with higher onsets compared to the equivalent fragments formed from [(FeTPP)2OH]+. Copyright © 2009 John Wiley & Sons, Ltd. |
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| Keywords: | electrospray ionization mass spectrometry bridged metalloporphyrin dimer ions collision‐induced ion dissociation [(FeTPP)2OH]+ [(FeTPP)2Cl]+ |
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