Ion pairs from redox reaction of decamethylchromocene with cyclopentadienyltitanium trichlorides

► Decamethylchromocene donates one electron to half-sandwich titanocene trichlorides. ► 1H NMR identified chromocenium, titanates, and toluene of crystallization. ► Crystal structures revealed short Ti-Cg distances and long Ti-Cl bonds in titanates. ► DFT calculation: the donated electron is delocalized in Ti-(C5Me5) bonding orbitals.