The syntheses of meridionally ligated tricarbonyl complexes (PNP)Mn(CO)(3) and (PNP)Re(CO)(3) are described (PNP=[2-P(CHMe2)(2)-4-MeC6H3](2)N-). Cyclic voltammograms show reversible one-electron redox couples for both parent compounds (-0.34 V vs CP(2)Feo(0/+) for (PNP)Mn(CO)(3), -0.25 V vs CP2Fe0/+ for (PNP)Re(CO)(3)), and chemical oxidation with AgOTf results in formation of the corresponding paramagnetic triflate salts [(PNP)Mn(CO)(3)]OTf and [(PNP)Re(CO)(3)]OTf. Electron paramagnetic resonance spectra and computational results indicate that this event is primarily ligand centered; allylation of the organic ligand moiety of [(PNP)Mn(CO)(3)]OTf with allyltributylstannane is consistent with this assignment. The oxidation (PNP)Mn(CO)(3) to [(PNP)Mn(CO)(3)]OTf results in a shift in average CO stretching frequency of 30 cm(-1); protonation of (PNP)Mn(CO)(3) with TfOH to form [(PNHP)Mn(CO)(3)]OTf results in a similar magnitude shift.