Reaction of a potential NCN-pincer ligand, viz. 1,3-di(phenylazo)benzene (L), with [Rh(PPh(3))(3)Cl] affords, via a C-H bond activation, an interesting dinuclear Rh(II) complex (1), and with RhCl(3)·3H(2)O affords a mononuclear Rh(III) complex (2) containing a catalytically useful Rh-OH(2) fragment.