Abstract
The use of fast atom bombardment mass spectrometry (FAB-MS) to study a series of porphyrins (H 2P) and metalloporphyrins (MetP) was investigated. Methods of sample preparation and choice of a suitable matrix for optimum FAB-MS studies of porphyrins are described. Rates of demetallation and the redox chemistry of such compounds were examined and the solution chemistry of metalloporphyrins was compared with their behaviour in FAB-MS. Such considerations lead to an understanding of various aspects of the physico-chemical events occurring in the FAB matrix. By using FAB matrices with different electronic or acidic properties, it was demonstrated that demetallation can occur either by proton displacement or one-electron reduction of the metal. It was also found that demetallation by protons in FAB-MS correlates with the stability index (S i ). One-electron reductions of Ag(II)P and Cu(II)P were shown to occur via an excited-state intermediate. Consideration of fragmentation and metal ion uptake by two multi-component porphyrins in FAB-MS also confirmed the previously assigned geometry of these compounds.
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