Ruthenium bis(beta-diketonato) complexes have been prepared at both the Ru-II and Ru-III oxidation levels and with protonated and deprotonated pyridine-imidazole ligands. Ru-II(acac)(2)(py-imH) (1), [Ru-III(acac)(2)(py-imH)]OTf (2), Ru-III(acac)(2)(py-im) (3), Ru-II(hfac)(2)(py-imH) (4), and [DBU-H][Ru-II(hfac)(2)(py-im)] (5) have been fully characterized, including X-ray crystal structures (acac 2,4-pentanedionato, hfac = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionato, py-imH = 2-(2'-pyridyl)imidazole, DBU 1,8-diazabicyclo[5.4.0]undec-7-ene). For the acac-imidazole complexes 1 and 2, cyclic voltarnmetry in MeCN shows the Ru-III/II reduction potential (E-1/2) to be -0.64 V versus Cp2Fe+/0. E-1/2 for the deprotonated imidazolate complex 3 (-1.00 V) is 0.36 V more negative. The Ru-II bis-hfac analogues 4 and 5 show the same Delta E-1/2 = 0.36 V but are 0.93 V harder to oxidize than the acac derivatives (0.29 and -0.07 V). The difference in acidity between the acac and hfac derivatives is much smaller, with pK(a) values of 22.1 and 19.3 in MeCN for 1 and 4, respectively. From the E-1/2 and pKa values, the bond dissociation free energies (BDFEs) of the N-H bonds in 1 and 4 are calculated to be 62.0 and 79.6 kcal mol(-1) in MeCN - a remarkable difference of 17.6 kcal mol(-1) for such structurally similar compounds. Consistent with these values, there is a facile net hydrogen atom transfer from 1 to TEMPO. (2,2,6,6-tetramethylpiperidine-1-oxyl radical) to give 3 and TEMPO-H. The Delta G degrees for this reaction is -4.5 kcal mol(-1). 4 is not oxidized by TEMPO. (AGO = +13.1 kcal mol(-1)), but in the reverse direction TEMPO-H readily reduces in situ generated Ru-III(hfaC)(2)(py-im) (6). A Ru-II-imidazoline analogue of 1, Rut(acac)(2)(py-imnH) (7), reacts with 3 equiv of TEMPO. to give the imidazolate 3 and TEMPO-H, with dehydrogenation of the imidazoline ring.