One-electron and multielectron reductions of 2,7,12,17-tetrapropylporphycene (H(2)TPrPc) and its Fe, Co, Ni, Cu, and Sn complexes in 2-PrOH solutions have been studied by radiolytic techniques. Formation and decay of intermediates formed upon one-electron reduction have been followed by kinetic spectrophotometric pulse radiolysis, and the absorption spectra of stable reduction products have been recorded following gamma-radiolysis. H(2)TPrPc; and Sn(IV)TPrPc are reduced to the cc-radical anions and then to the dianions, which are stable in alkaline 2-PrOH. In neutral or acidic solutions, the pi-radical anions undergo proton-enhanced disproportionation and the dianions undergo protonation. With the transition metal complexes, redox reactions of Fe-III/Fe-II and Co-III/Co-II have been observed. The porphycenes of Fe-II, Co-II, Ni-II, and Cu-II are reduced in most cases to form the pi-radical anions, M(II)Pc(.-). The exception is the case of the Co(II)Pc, which forms Co(II)Pc(.-) in alkaline 2-PrOH but yields a short-lived Co(I)Pc in neutral 2-PrOH, Cu(II)Pc(.-) has some Cu-I character, resulting in rapid demetallation in acidic solutions. The radical anions M(II)Pc(.-) also undergo proton-enhanced disproportionation to yield M(II)PcH(2).