The present work deals with the imidorhenium(V) complexes of type [ReCl 3(NC 6H 4Y- p)(L)], with Y = OCH 3( 1d), CH 3( 1c), H( 1b), Cl( 1a) where L is the pyridylimine Schiff base ligand obtained from facile condensation of pyridine-2-carboxaldehyde and p-phenylenediamine. Structural authentication of one representative ( 1d) reveals meridional disposition of three Cl atoms around the metal center in a distorted octahedral ReCl 3N 3 coordination environment. Re–N pyridine bond lying trans to Re NC 6H 4Y- p motif is lengthened by ∼0.2 Å compared to Re–N imine bond and is attributed to trans influence of imide nitrogen. The complexes, 1 are reactive towards dilute aqueous nitric acid furnishing amide bound hexavalent rhenium complexes, 2. Six lines EPR spectra have been recorded for 2 in solution phase at ambient condition (g iso ∼ 1.945, A av ∼ 493 G) and magnetic susceptibility measurement indicates strong orbital coupling consistent with one electron paramagnetic nature (∼1.45 μ B). Re VI/Re V responses for 1 appear at higher potential (∼0.95 V) that those observed for 2 (∼0.12 V). Type 2 complexes are reduced (low Re VI/Re V reduction potential, +0.15 V) by N 2 H 5 + and NH 3OH + species under mild condition to regenerate 1. The reduction with N 2 H 5 + is nearly five times faster than NH 3OH +. Rate study suggests an associative pathway (Δ H ≠ = 11.61 kcal mol −1, Δ S ≠ = −31.22 eu using N 2 H 5 + and Δ H ≠ = 10.74 kcal mol −1, Δ S ≠ = −37.30 eu using NH 3OH +) for amide → imine transformation. No such analogous amide → imine conversion has yet been achieved in metal free environment, accentuating the exclusive electronic role of variable metal valence. Further, the oxo complex, 6 does not exhibit intramolecular ligand oxidation suggesting decisive electronic role of the coligands (oxo/arylimido) in stabilizing higher metal valence.