The new class of tert-butyl mercapto compounds, Ti(L)Cl2(tBuS)2 (L = diars, dmpe, dppe), has been synthesized and characterized. The X-ray crystal structure of Ti(diars)Cl2(tBuS)2 (1) shows that the Ti(IV) atom has a distorted octahedral geometry with trans chlorides and cis tert-butyl mercapto units. The structures of the other complexes are similar based on spectroscopic (NMR, IR) evidence. Crystal data for (1): C18H34As2Cl2S2Ti, M = 583.24, trigonal space group P3121 (No. 152), a = b = 16.892(5) Å, c = 8.492(2) Å, U = 2098.4 Å3, Z = 3, Dc = 1.389 gcm-3, μ = 29.841 cm-1, λ(MoKα) = 0.71069 Å (graphite monochromator). Refinement of 948 observed (1371 unique measured; I > 3σ(I) reflections gave a final R = 0.0462 and Rw = 0.0597.