The reduction of ReO4- with 2-hydrazinopyridine dihydrochloride and PPh3 gives [ReCl(PPh3)(2)(NHNC5H4N)(HNNC5H4N)]Cl-2 (2). A similar reaction using 2-hydrazino-2-imidazoline and PPh3 in methanol hydrochloric acid allows the preparation of [ReCl3(PPh3)(2)(NNC3H4N2)] (3). The reaction of the Re(III) complex [ReCl3(NNC5H4NH)(HNNC5H4N)] (1), with 2-(Ph2P)C6H4SH in methanol yields [Re{2-(Ph2P)C6H4S}{2-(Ph2PO)C6H4S}(NNC5H4N)(HNNC5H4N)] (4) and [Re{2-(Ph2P)C6H4S}(2)(NNC5H4N)] (5). The same precursor with 2-(Ph2PO)-6-(Me3Si)C6H3SH gives [ReCl{2-(Ph2PO)-6-(Me3Si)C6H3S}(NNC5H4N)(HNNC5H4N)] (6) and with PhP(C6H4SH2)(2) yields [Re{PhP(C6H4S-2)(2)}(NNC5H4N)(HNNC5H4N)] (7). Crystal data: 2, C46H39N6P2Cl3Re, orthorhombic, Pnma, a = 19.6381(7) Angstrom, b = 15.1861(6) Angstrom, c = 15.0711(5) Angstrom, V = 4494.6(3) Angstrom(3), Z = 6, 5646 reflections, R = 0.0655; 4, C46H37N6OP2S2Re, triclinic, P (1) over bar, a = 9.4233(2) Angstrom, b = 15.8308(3) Angstrom, c = 16.3530(2) Angstrom, alpha = 61.88(10)degrees, beta = 80.9220(10)degrees, gamma = 85.1350(10)degrees, V = 2124.40(7) Angstrom(3), Z = 2, 8728 reflections, R = 0.0757; 5, monoclinic, P2(1)/c, a = 10.0006(2) Angstrom, b = 18.1857(1) Angstrom, c = 19.8595(2) Angstrom, beta = 94.09(1)degrees, V = 3598.08(8) Angstrom(3), Z = 4, 8406 reflections, R = 0.0359.