One electron paramagnetic parent osazone complex of rhodium of type trans-Rh((LH2)-H-NHPh)(PPh3)(2)Cl-2 (1), defined as an osazone anion radical complex of rhodium(III), trans-Rh-III((LH2 center dot-)-H-NHPh)(PPh3)(2)Cl-2, 1((t-RhL center dot)), with a minor contribution (similar to 2%) of rhodium(II) electromer, trans-Rh-II((LH2)-H-NHPh)(PPh3)(2)Cl-2, 1((t-Rh center dot L)), and their nonradical congener, trans-[Rh-III((LH2)-H-NHPh)(PPh3)(2)Cl-2]I-3 ([t-1]I-+(3)-), have been isolated and are substantiated by spectra, bond parameters, and DFT calculations on equivalent soft complexes [Rh((LH2)-H-NHPh)(PMe3)(2)Cl-2] (3) and [Rh((LH2)-H-NHPh)(PMe3)(2)Cl-2](+) (3(+)). 1 is not stable in solution and decomposes to [t-1](+) and a new rhodium(I) osazone complex, [Rh-I((LH2)-H-NHPh)(PPh3)Cl] (2). 1 absorbs strongly at 351 nm due to MLCT and LLCT, while [t-1](+) and 2 absorb moderately in the range of 300-450 nm, respectively, due to LMCT and MLCT elucidated by TD-DFT calculations on 3((t-RhL center dot)), [t-3](+), and Rh-I((LH2)-H-NHPh)(PMe3)Cl (4). EPR spectra of solids at 295 and 77 K, and dichloromethane-toluene frozen glass at 77 K of 1 are similar with g = 1.991, while g = 2.002 for the solid at 25 K. The EPR signal of 1 in dichloromethane solution is weaker (g = 1.992). In cyclic voltammetry, 1 displays two irreversible one electron transfer waves at +0.13 and -1.22 V, with respect to Fc(+)/Fc coupling, due to oxidation of 1((t-RhL center dot)) to [t-1](+) at the anode and reduction of rhodium(III) to rhodium(II), i.e., [t-1](+) to electromeric 1((t-Rh center dot L)) at the cathode.