Following the track of the useful titanocene [Ti(eta(5)-C5H5)(2)Cl] reagent in organic synthesis, the related half-sandwich titanium(III) derivatives [Ti(eta(5)-C5R5)Cl-2] are receiving increasing attention in radical chemistry of many catalyzed transformations. However, the structure of the active titanium(III) species remains unknown in the literature. Herein, we describe the synthesis, crystal structure, and electronic structure of titanium(III) aggregates of composition [{Ti(eta(5)-C5Me5)Cl-2}(n)]. The thermolysis of [Ti(eta(5)-C5Me5)Cl2Me] (1) in benzene or hexane at 180 degrees C results in the clean formation of [{Ti(eta(5)-C5Me5)Cl(mu-Cl)}(2)] (2), methane, and ethene. The treatment of 1 with excess pinacolborane in hexane at 65 degrees C leads to a mixture of 2 and the paramagnetic trimer [{Ti(eta(5)-C5Me5)(mu-Cl)(2)}(3)] (3). The X-ray crystal structures of compounds 2 and 3 show Ti-Ti distances of 3.267(1) and 3.219(12) angstrom, respectively. Computational studies (CASPT2//CASSCF and BS DFT methods) for dimer 2 reveal a singlet ground state and a relatively large singlet-triplet energy gap. Nuclear magnetic resonance spectroscopy of 2 in aromatic hydrocarbon solutions and DFT calculations for several [{Ti(eta(5)-C5Me5)Cl-2}(n)] aggregates are consistent with the existence of an equilibrium between the diamagnetic dimer [{Ti(eta(5)-C5Me5)Cl(mu-Cl)}(2)] and a paramagnetic tetramer [{Ti(eta(5)-C5Me5)(mu-Cl)(2)}(4)] in solution. In contrast, complex 2 readily dissolves in tetrahydrofuran to give a green-blue solution from which blue crystals of the mononuclear adduct [Ti(eta(5)-C5Me5)Cl-2(thf)] (4) were grown.