The relevant N,N-coordinating ligands are RN=(H)-C(H)=NR (general abbreviation D, specific abbreviations D-1 and D-2 for R = cyclohexyl and p-tolyl, respectively) and [RN=C(H)-C(=O)-NR](-) (abbreviations A, A(1), A(2). Oxidation of cis- and trans-(RuD2Cl2)-D-II by aqueous cerium(IV) (H2O2 can also be used for trans-RuD2Cl2) affords in excellent yield the amide complexes cis- and trans-Ru(III)DACl(2) with retention of parental isomeric structure. Spectral and magnetic characterization data of the complexes are reported along with the X-ray structures of cis-RuD12Cl2 . PhMe and cis-RuD(1)A(1)Cl(2) . CH2Cl2. The ruthenium(III)-ruthenium(II) couples of the complexes follow E(1/2) systematics (other things remaining the same in each case) : geometry, cis > trans; ligand, D > A; substituent, p-tolyl > cyclohexyl. The (RuD2Cl2+)-D-III moiety has been electrogenerated in solution, and cis- [(RuD2Cl2)-D-III-Cl-1]ClO4 has been isolated and characterized in the pure state. The conversion RuD2Cl2 --> RuDACl(2) actually occurs via RuD2Cl2+, which reacts with water, affording the amide complex. The reaction is first order with respect to both RuD2Cl2+ and H2O, and the activation parameters are Delta h(double dagger) = 12.5 kcal mol(-1) and Delta S-double dagger = -29.8 eu in the case of trans-(RuD2Cl2)-Cl-2.