We present the results of multiple temperature 1 H NMRD and variable temperature and pressure, multiple field 1 7 O NMR studies on the gadolinium(III) complex of the tripod ligand H 6 ttaha {N-tris(2-aminoethyl)amine-N ,N ,N ,N ,N ,N -hexaacetate) in aqueous solution. Of the ten donor atoms, seven are coordinated to the center metal, leaving one of the tripod legs free. The coordination number is completed to nine by two water molecules (q = 2), as confirmed by the value of the scalar coupling constant A/ = (-3.5±0.1) 10 6 rad s - 1 . The higher number of inner-sphere water molecules causes a higher 1 H relaxivity as compared to commercial gadolinium(III) based MRI contrast agents. The water exchange rate was determined as k 2 9 8 e x = (8.6±0.6) 10 6 s - 1 . The enthalpy and volume of activation are ΔH ≠ = (40.4 ± 1.4) kJ mol - 1 and ΔV ≠ = (2.9 ± 1.0) cm 3 mol - 1 , respectively, the latter indicating a dissociatively activated interchange I d mechanism. The water exchange is unexpectedly fast for an exchange reaction that is not limiting dissociative D; this lability is interpreted as being due to the higher number of inner-sphere water molecules.