Synthesis of tert-butyl mercapto complexes of titanium(IV). X-ray crystal structure of Ti(diars)Cl2 (tBuS)2

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 ų, Z = 3, D_c = 1.389 gcm^?3, μ = 29.841 cm^?1, λ(MoK_α) = 0.71069 Å (graphite monochromator). Refinement of 948 observed (1371 unique measured; I > 3σ(I) reflections gave a final R = 0.0462 and R_w = 0.0597.