Claisen condensation of acetyl ruthenocene with the appropriate methyl ester, RCOOMe, under the influence of the hindered base lithium diisopropylamide gave the β-diketones (RcCOCH2COR) 1-ruthenocenyl-4,4,4-trifluorobutane-1,3-dione (ruthenocenoyltrifluoroacetone, 1, R = CF3; pKa′ = 7.36 ± 0.03), 1-ruthenocenylbutane-1,3-dione (ruthenocenoylacetone, 2, R = CH3; pK a′ = 10.22 ± 0.01), 1-phenyl-3-ruthenocenylpropane-1,3-dione (benzoylruthenocenoylmethane, 3, R = C6H5; pKa′ = 11.31 ± 0.03), 1-ferrocenyl-3-ruthenocenylpropane-1,3-dione (ferrocenoylruthenocenoylmethane, 4, R = Fc = (C5H5)Fe(C5H4) = ferrocenyl; pKa′ = ca. 12.8), and 1,3-diruthenocenylpropane-1,3-dione (diruthenocenoylmethane, 5, R = Rc = (C5H5)Ru(C5H4) = ruthenocenyl; pKa′ = ca. 12.7). The group electronegativity of the ruthenocenyl group, χRc = 1.89 on the Gordy scale, was obtained from the linear relationship between IR carbonyl stretching frequencies of a series of methyl esters, RCOOMe, and χR. A 1H NMR kinetic study of the enol−keto interconversion resulted in accurate equilibrium constants, Kc, for this equilibrium, as well as forward and reverse rate constants of the isomerization process. Cyclic voltammetry in CH3CN/N(nBu)4PF6 utilizing a glassy-carbon electrode showed the ruthenocene center exhibited, in contrast to the ferrocene center, irreversible electrochemistry. The multiple peak anodic (oxidation) potentials observed are a consequence of slow isomerization kinetics and made peak assignments for the keto and enol isomers possible. The kinetics of enol to keto isomerization for 4 was also studied by cyclic and Osteryoung square wave voltammetry; obtained rate constants were mutually consistent with those obtained by the 1H NMR technique. Kinetic rate constants, Kc, and pKa′ and Ep,a were related to χR values of the R groups in RcCOCH2COR.