Decamethylchromocene [formula] reacted with cyclopentadienyltitanium trichlorides in toluene to precipitate yellow finely crystalline ion pairs. Evidence for the chromocenium cation and titanate anions was obtained by paramagnetic 1H NMR spectra of [formula]1–6 in CD2Cl2. The resonance of the cation was invariant at theta 6.9 ppm whereas resonances of the titanate anions were shifting in response to the number of methyl groups (theta 10.5–8.4 ppm (CpMe) and theta 26.6–39.0 ppm (CpH)). The presence of toluene of crystallization in 1–6 was observed by 1H NMR spectra, and in the crystal structure of 6. Crystallization of 6 from tetrahydrofuran afforded solvent-free crystals of 6A. In crystal structures of both 6 and 6A [formula] the titanate anion possessed shorter Ti–Cg distances and longer Ti–Cl bonds than the neutral species.