Cycloreversion and other gas-phase reactions of neutral and cationic pyrrolidine-fused chlorins and isobacteriochlorins under ion bombardment and electrospray.
Neutral and cationic pyrrolidine-fused chlorins and isobacteriochlorins derived from meso-tetrakis(pentafluorophenyl)porphyrin undergo cycloreversion reactions in the gas phase, either when desorbed from a liquid matrix by ion bombardment or when electrosprayed. Cycloreversion occurs through loss of either neutral or charged moieties, with and without hydrogen and methyl radical migration, and both as high- and low-energy collision processes. For the doubly charged isobacteriochlorin, one-electron reduction with methyl loss occurs under ion bombardment and electrospray, through hypervalent pyrrolidinium radical formation.
Mass Spectrometry Laboratory, Department of Chemistry, University of Aveiro, Campus de Santiago, 3810-193 Aveiro, Portugal.
Raul A
RA
Izquierdo
Cristina M
CM
Barros
M Graça
MG
Santana-Marques
A J Ferrer
AJ
Correia
Ana M G
AM
Silva
Augusto C
AC
Tomé
Artur
A
Silva
M Graça P M S
MG
Neves
J A S
JA
Cavaleiro
D011166:Porphyrins / Q000032:analysis / Q000737:chemistry*; D011759:Pyrrolidines / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization
D011166:Porphyrins; D011759:Pyrrolidines; C452434:isobacteriochlorin; C006969:chlorin; C032519:pyrrolidine