Sulfonated metalloporphyrins (Me-TSPP, where Me = Cr(III), Mn(III), Fe(III), and Mn(Il)) comprise a well-characterized series of water-soluble paramagnetic complexes with electron spins of S = 3/2, 2, 5/2, and 5/2, respectively, which provide important model systems for mechanistic studies of paramagnetic NMR relaxation in solution. Previous studies of Mn(III), Fe(III), and Mn(II)-TSPP have uncovered relaxation mechanisms which differ qualitatively from each other and exhibit numerous unexpected features. In this study, Cr(III)-TSPP was examined as a model system for the d(3) S = 3/2 electron configuration. Magnetic relaxation dispersion (MRD) profiles of the water proton R, were measured as a function of pH between pH 1 and pH 9. In acid samples, R-1 results from acid-catalyzed prototropic chemical exchange involving the Cr(III)-TSPP center dot 2H(2)O. In neutral and basic solution, this species deprotonates, and base-catalyzed prototropic exchange becomes important. The pH 1 data were analyzed quantitatively using theory that accounts for the role of the permanent zero field splitting (zfs) tensor and for the effects of Brownian reorientation. Two levels of theory were employed: (1) spin dynamics simulation, which accurately describes the effects of Brownian reorientation on the spin wave functions, and (2) the "constant Hs'' approximation, which incorporates the effects of multiexponential electron spin relaxation and facilitates the physical interpretation of the relaxation mechanism. It was found that neither level of theory alone provides a fully satisfactory quantitative description of the data due to the fact that both reorientational modulation of the spin wave functions and multiexponential electron spin relaxation are important. The zero field splitting parameter, D = 0.27 cm(-1), is well defined by the data and was measured.