Conventional and stopped-flow spectrophotometry was used to to study the kinetics of ligand substitution in a number of bis(N-alkylsalicylaldiminato)oxovanadium(IV) complexes (=VO(R-X-sal)(2)) by 1,1,1-trifluoropentane-2,4-dione (=Htfpd) in acetone, according to the following reaction: VO(R-X-sal)(2) + 2Htfpd --> VO(tfpd)(2) + 2R-X-salH. The acronym R-X-salH refers to N-alkylsalicylaldimines with substituents X = H, Cl, Br, CH3, and NO2 in the 5-position of the salicylaldehyde ring and N-alkyl groups R = n-propyl, isopropyl, phenyl, and neopentyl. Under excess conditions ([Htfpd](0) much greater than [VO(R-X-sal)(2)](0)), substitution by Htfpd occurs in two observable steps, as characterized by pseudo-first-order rate constants k(obsd(1)) and k(obsd(2)). Both rate constants increase linearly with [Htfpd](0) according to k(obsd(1)) = k(s(1)) + k(1)[Htfpd](0) and k(obsd(2)) = k(s(2)) + k(2)[Htfpd](0), with k(s(1)) and k(s(2)) describing small contributions of solvent-initiated pathways. Depending on the nature of R and X, second-order rate constants k(1) and k(2) lie in the range 0.098-0.87 M-1 s(-1) (k(1)) and 0.022-0.41 M-1 s(-1) (k(2)) at 298 K. For ligand substitution in the system VO(n-propyl-sal)(2)/Htfpd, the activation parameters DeltaH(double dagger) = 35.8 +/- 2.8 kJ mol(-1) and DeltaS(double dagger) = -146 +/- 23 J K-1 mol(-1) (k(1)) and DeltaH(double dagger) = 40.2 +/- 1.3 kJ mol(-1) and DeltaS(double dagger) = -142 +/- 11 J K-1 mol(-1) (k(2)) were obtained. The Lewis acidity of the complexes VO(n-propy]-X-sal)(2) with X = H, Cl, Br, CH3, and NO2 was quantified spectrophotometrically by determination of equilibrium constant K-py, describing the formation of the adduct VO(n-propyl-X-sal)(2)(.)pyridine. The adduct VO(tfpd)(2)(.)n-propyl-salH, formed as product in the system VO(n-propyl-sal)(2)/Htfpd, was characterized by its dissociation constant, K-D = (3.30 +/-0.10) X 10(-3) M. The mechanism suggested for the two-step substitution process is based on initial formation of the adducts VO(R-X-sal)(2)(.)Htfpd (step 1) and VO(R-X-sal)(tfpd)(.)Htfpd (step 2).