New Organometallic Heteronuclear μ-Oxo Complexes. X-ray Structure of [Cp*₃Ti₃Cl(μ-O₂SO₂)](μ-O)₃·C₆H₅CH₃

The reaction of [Cp*TiCl(μ-O)]₃ (1) (Cp* = η⁵-C₅Me₅) with anhydrous silver salts of a variety of oxyanions (SO₄²⁻, CrC₄²⁻, NO₃⁻, and ReO₄⁻) in organic solvents leads to the isolation of the compounds [Cp*₃Ti₃(EO₄)_x-Cl_y](μ-O)₃ [x = y = 1. E = Cr (2), S (3); x = 3, γ = 0, E = Re (4)], [Cp*Ti₃(NO₃)_xCl_3-x](μ-O)₃ [x = 1 (5), 3 (6)], and [Cp*₃Ti₃(CrO₄)L](μ-O)₃ [L = NO₃ (7), ReO₄ (8)]. The crystal structure of [Cp*₃Ti₃Cl(μ-SO₄)](μ-O)₃ (3) determined by X-ray analysis shows that the complex crystallizes solvated with one molecule of toluene in the space group P1; a = 8.943(2) Å, b = 11.912(2) Å, c = 19.259(4) Å, a =72.74(3)°, β = 89.57(3)°, γ = 89.62(3)°, Z = 2, R = 0.078, and R_w = 0.105. The molecule contains a Ti₃O₃ core where a μ-O₂SO₂ ligand bridges two titanium atoms separated by 3.182(2) Å, a distance substantially shorter than the other two, 3.317(2) and 3.304(3) Å respectively.