Organoaluminum and -gallium thiolates. 1. Synthetic and x-ray structural studies

Article abstract of DOI:10.1021/om00006a040

Organoaluminum and -gallium thiolates are prepared in high yield by the reaction of triorganoaluminum and -gallium derivatives with thiols. In this way, [Mes₂Al(μ-SBz)]₂ (Mes = 2,4,6-Me₃C₆H₂; Bz = CH₂C₆H₅) (1), [Me₂Al(μ-SSiPh₃)]₂ (2), [Mes₂Al(μ-SPh)]₂ (3), {Me₂Al-[μ-S(2-t-BuC6H₄)]}₃ (4), {Me₂Al[μ-S(2-Me₃Si)C₆H₄]} ₃ (5), {Me₂Al[μ-S(2-i-PrC₆H₄)]}₃ (6), {i-Bu₂Al[μ-S(2,4,6-i-Pr₃C₆H ₂)]}₃ (7), {Me₂Al[μ-S(2,6-Me₂C₆H₃)]} ₄ (8), and {Me₂Ga[μ-S(2,6-Me₂C₆H₃)]} ₄ (9) were prepared and crystallographically characterized. The dimethyl- and dimesitylaluminum thiolates 1-3 were determined to be dimeric with four-membered (AlS)₂ rings. The structure of 1 was determined in space group P2₁/n (No. 14): a = 10.660(4) A?, b = 12.268(2) A?, c = 17.793(3) A?, β = 106.94(2)°, Z = 4, R = 6.7%, and R_w = 6.1%. The structures of 2 and 3 were determined in space group P1 (No. 2): a = 9.077(2) A?, b = 13.847-(3) A?, c = 16.724(4) A?, α = 101.08(2)°, β = 95.34(2)°, γ = 103.38(2)°, Z = 2 (dimers), R = 5.2%, and R_w = 5.1% for 2, and a = 11.068(5) A?, b = 12.470(3) A?, c = 17.654(5) A?, α = 90.97(2)°, β = 107.77(3)°, γ = 112.23(3)°, Z = 4, R = 5.9%, and R_w = 4.8% for 3. The dialkylaluminum thiolates, 4-7, were found to be trimeric in the solid state. The structure of 4 was determined in space group P2₁/c (No. 14), a = 9.324(7) A?, b = 18.632(5) A?, c = 23.959(9) A?, β = 98.31(5)°, Z = 4 (trimers), R = 7.6%, and R_w = 5.2%; 5 in space group P1 (No. 2), a = 10.149(4) A?, b = 14.427(5) A?, c = 15.159(4)A?, α = 88.19(3)°, β = 89.39(3)°, γ = 88.57(3)°, Z = 2 (trimers), R = 5.0%, and R_w = 5.0 %; 6 in space group P1 (No 2) a = 12.538(5) A?, b = 13.180(2) A?, c = 13.873(2) A?, α = 74.38(1)°, β = 64.18(2)°, γ = 69.44(2)°, Z = 2 (trimers), R = 5.2% and R_w = 4.4%; and 7 in space group P2₁/c (No. 14), a = 13.935(2) A?, b = 22.563(4) A?, c = 25.044(4) A?, β = 101.44(1)°, Z = 4 (trimers), R = 12.5%, and R_w = 14.2%. The sulfur atoms in 7 are in a planar environment. Compounds 8 and 9 are tetrameric with eight-membered (MS)₄ (M = Al, Ga) ring systems. They are isomorphous, and their structures were determined in space group P1 (No. 2). For 8 a = 8.555(1) A?, b = 11.869(1) A?, c = 12.688(1) A?, α = 96.546(8)°, β = 106.34(1)° γ = 109.06(1)°, Z = 2, R = 5.0%, and R_w = 5.2%, and for 9 a = 8.525(2) A?, b = 11.805(3) A?, c = 12.714(4) A?, α = 96.36-(2)°, β = 106.46(2)°, γ = 108.90(2)°, Z = 2, R = 6.1%, and R_w = 6.6%.