Direct observation of 47,49Ti resonances in a series of TiX4 (X = Cl, Br, I, OPri, NEt2), (C5H5)2TiX2 (X = F, Cl, Br, I, N3, NCS), and TiX62− (X = F, Br) complexes is reported. 47,49Ti nuclei are equally sensitive to changes of halogen ligands in the (C5H5)2MX2 series as the 91Zr nucleus. The inverse halogen dependence of δ(47,49Ti) is extended and placed on a more quantitative basis in the (C5H5)2TiX2 systems. The TiF62− ion reveals septets for both the 47Ti and 49Ti resonances, with 1J47Ti19F = 1J49T19F = 34.0 Hz. Spin-lattice relaxation times are reported for TiCl4 and TiF62−. A detailed study of TiCl4 reveals the dominance of a quadrupolar relaxation mechanism. Correlation times calculated from the Gierer and Wirtz relationship combined with observed T1 results allow the quadrupole coupling constants for 47,49Ti nuclei to be estimated as 2.8 and 2.4 MHz, respectively.