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 with4630 reflections, R ) 0.0525; 10, C 48 H 39 N 3 OSP 2 ClRe, triclinic, P1 h, a ) 10.842(2) Å, b ) 13.660 (3) Å, c ) 17.665(4) Å, R ) 86.37(3)°, β ) 89.93(3)°, γ ) 77.22(3)°, V ) 2080.2(10) Å 3 , Z ) 2, 4329 reflections, R ) 0.0437; 11, C 12 H 9 N 6 OS 3 Re, orthorhombic, Pbca, a ) 8.240(2) Å, b ) 13.373(3) Å, c ) 29.388-(6) Å, V ) 3238.4(16) Å 3 , Z ) 8, 1400 reflections, R ) 0.0512; 12, C 31 H 26 N 6 S 3 PCl 2 Re, triclinic, P1 h, a ) 9.224-(2) Å, b ) 12.050(2) Å, c ) 17.665(4) Å, R ) 89.25(3)°, β ) 85.70(3)°, γ ) 67.94(3)°, V ) 1604.0(8) Å 3 , Z ) 2, 3592 reflections, R ) 0.0697.