The reactions of ammonium perrhenate, HCl(aq), and the phosphinothiol ligands (2-HSC6H4)P(C6H4X)(2), where X = H or SH [abbreviated P-(SH)(x) (x = 1, 3)], in alcohol have led to the isolation of a series of rhenium complexes containing the {M(P-S-x)(2)} core, represented by [Re{P(C6H4S)(3)}{P(C6H4S)(2)(C6H4SH)}] (1), [ReOCl-{OP(C6H5)(2)(C6H4S)}{P(C6H5)(2)(C6H4S)}] (3), and [ReOCl{OP(C6H5)(2)(2-SC6H3-3 -SiMe3)}(2)] (5). The reaction of 1 with NEt3 results in the formation of [HNEt3] [Re{P(C6H4S)(3)}2] (2) by deprotonation of a thiol ligand. The reaction of ammonium perrhenate with P-(SH) also led to the isolation of the binuclear species [ReOCl{OP-(C6H5)(2)(2-SC6H3-3 -SiMe3)}(2)] (4). Crystal data : 2, C43H42NP2S6Cl2Re, monoclinic, P2(1)/c, a = 14.2484(2) Angstrom, b = 15.3108(1) Angstrom, c = 19.5121(2) Angstrom, beta = 90.366(1)degrees, V = 4256.56(8) Angstrom(3), Z = 2, 26410 reflections, R = 0.0605; 3, C36H28O2P2S2ClRe, triclinic, P (1) over bar, a = 9.3427(1) Angstrom, b = 11.9075(1) Angstrom, c = 16.8504(1) Angstrom, alpha = 98.177(1)degrees, beta = 104.132(1)degrees, gamma = 109.000(1)degrees, V = 1667.79(2) Angstrom(3), Z = 2, 7567 reflections, R = 0.0333; 4, C36H28O5P2S2Re2, monoclinic, P2(1)/n, a = 10.6714(1) Angstrom, b = 24.0076(2) Angstrom, c = 13.3610(1) Angstrom, beta = 93.65(1)degrees, V = 3416.51(4) Angstrom(3), Z = 4, 8073 reflections, R = 0.0469; 5, C44H47NO3Si2P2S2ClRe, triclinic, P (1) over bar, a = 10.1616(2) Angstrom, b = 14.7095(3) Angstrom, c = 17.0744(3) Angstrom, alpha = 89.108(1)degrees, beta = 83.634(1)degrees, gamma = 70.901(1)degrees, V = 2396.21(8) Angstrom(3), Z = 2, 6175 reflections, R = 0.0837.