Two new Ti-eta(6)-arene complexes [(DMSC)Ti{eta(6)-1,2.4-C6H3(SiMe3)(3)}] (6) and [(DMSC)Ti{eta(6)-1,3,5-C6H3Bu3t}] (7) containing 1,2-alternate, Me2Si-bridged p-tert-butylcalix[4]arene (DMSC) ancillary ligand have been synthesized. The solid-state structure of 6 revealed a highly folded arene ligand [with a dihedral angle of 29.7(7)degrees] and suggests that 6 is better described as a 7-titananorbornadiene species. Both 6 and 7 are efficient catalysts for highly regioselective [2 + 2 + 2] cycloaddition of terminal alkynes to yield 1,2,4-substituted benzenes. Kinetic studies of the catalytic [2 + 2 + 2] cycloaddition of Me3SiC equivalent to CH revealed first-order dependence on [6] and [Me3SiC equivalent to CH]; and activation parameters, Delta H-double dagger = 14 kcal/mol, and Delta S-double dagger = -11 cal/mol K, that are consistent with an associative mechanism. The reaction rate is influenced by the steric requirements of both the alkyne and the eta(6)-arene compound. The high selectivity for 1,2,4-substituted benzene may be understood in terms of the directing influence of the DMSC ligand.