Unimolecular and bimolecular methane eliminations of TiMe(4) have been studied using nb initio molecular orbital theory. Geometry optimizations were performed with the 3-21G and HW3 (equivalent to the 6-31G*) basis sets. The energies were further evaluated with the MP2/HW3 calculations. We predict a high activation energy for unimolecular methane elimination but a low activation energy for bimolecular methane elimination. For Ti(CH2-CMe(3))4, neopentane elimination through alpha- and gamma-hydrogen abstractions has been studied with the 3-21G basis set. We predict an intrinsic preference for alpha-hydrogen abstraction over gamma-hydrogen abstraction. This preference is enhanced by the bulkiness of the alkyl ligands.