No 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](+).

Results are reported for experimental measurements of the room-temperature chemical reactions between ground-state Hg*+ ions and 16 important environmental and biological gases: SF6, CO, CO2, N2O, D2O, CH4, CH3F, O2, CH3Cl, OCS, CS2, NH3, C6F6, NO2, NO*, and C6H6. The inductively coupled plasma/selected-ion flow tube tandem mass spectrometer used for these measurements has provided both rate and equilibrium constants. Efficient electron transfer (>19%) is observed with CS2, NH3, C6F6, NO2, NO*, and C6H6, molecular addition occurs with D2O, CH4, CH3F, CH3Cl, and OCS, and SF6, CO, CO2, N2O, and O2 showed no measurable reactivity with Hg*+. Theory is used to explore the stabilities and structures of both the observed and unobserved molecular adducts of Hg*+, and reasonable agreement is obtained with experimental observations, given the uncertainties of the theory and experiments. A correlation is reported between the Hg*+ and proton affinities of the ligands investigated. Solvation of Hg*+ with formic acid was observed to increase the rate of electron transfer from NO* by more than 20%.