Synthesis and Characterization of Rhenium Thiolate Complexes. Crystal and Molecular Structures of [NBu4][ReO(H2O)Br4)]·2H2O, [Bu4N][ReOBr4(OPPh3)], [ReO(SC5H4N)3], [ReO(SC4H3N2)3][ReO(OH)(SC5H4N-3,6-(SiMe2But)2)2], [Re(N2COC6H5)(SC5H4N)Cl(PPh3)2], and [Re(PPh3)(SC4H3N2)3]

The syntheses and characterizations of six monomeric rhenium thiolate complexes and the structural characterization of two useful rhenium starting materials are presented. Pyridine-2-thiol (1) and its derivatives 3-(trimethylsilyl)pyridine-2-thiol (2), 3,6-bis(dimethyl-tert-butylsilyl)pyridine-2-thiol (3), and pyrimidine-2-thiol (4) were reacted with [Bu4N][ReOBr4(H2O)]·2H2O (5), [Bu4N][ReOBr4(OPPh3)] (6), [ReO2(C5H5N)4], and [Re{N2CO(C6H5)}Cl2(PPh3)2] to give [ReO(C5H4NS)3] (7), [ReO(C8H12NSiS)3] (8), [ReO(OH)(C11H20NSi2S)2] (9), [Re{N2CO(C6H5)}Cl(PPh3)2(C5H4NS)] (10), [ReO(C4H3N2S)3] (11), and [Re{P(C6H5)3}(C4H3N2S)3] (12). Crystal data: 5, C16H42NO4Br4Re, tetragonal, I4̄, a = 8.779(2) Å, b = 11.614(2) Å, c = 9.397(2) Å, β = 114.67(3)°, V = 870.7(4) Å3, Z = 2, 422 reflections, R = 0.0457; 6, C34H51NO2PBr4Re, triclinic, P1̄, a = 14.437(3) Å, b = 16.589(3) Å, c = 16.783(3) Å, α = 94.87(3)°, β = 97.62(3)°, γ = 93.80(3)°, V = 3957(2) Å3, Z = 4, 6141 reflections, R = 0.0758; 7, C15H12N3OS3Re, monoclinic, P21/c, a = 11.533(2) Å, b = 11.385(2) Å, c = 14.039(3) Å, β = 107.97(3)°, V = 1749.8(9) Å3, Z = 4, 1869 reflections, R = 0.0322; 9, C34H65N2O2S2Si4Re, triclinic, P1̄, a = 8.072(2) Å, b = 11.409(2) Å, c = 12.402(3) Å, α = 79.67(3)°, β = 74.05(3)°, γ = 86.18(3)°, V = 1080.2(5) Å3, Z = 1, 4630 reflections, R = 0.0525; 10, C48H39N3OSP2ClRe, triclinic, P1̄, a = 10.842(2) Å, b = 13.660 (3) Å, c = 17.665(4) Å, α = 86.37(3)°, β = 89.93(3)°, γ = 77.22(3)°, V = 2080.2(10) Å3, Z = 2, 4329 reflections, R = 0.0437; 11, C12H9N6OS3Re, orthorhombic, Pbca, a = 8.240(2) Å, b = 13.373(3) Å, c = 29.388(6) Å, V = 3238.4(16) Å3, Z = 8, 1400 reflections, R = 0.0512; 12, C31H26N6S3PCl2Re, triclinic, P1̄, a = 9.224(2) Å, b = 12.050(2) Å, c = 17.665(4) Å, α = 89.25(3)°, β = 85.70(3)°, γ = 67.94(3)°, V = 1604.0(8) Å3, Z = 2, 3592 reflections, R = 0.0697.