Preparations for 1,4,7,11,14,17-hexa-thiacycloeicosane, 1,4,7-trithiecan-9-ol, 1,11 -dioxa-4,8,14,18-tetrathia-cycloeicosane, 1 -oxa-4,8-dithiacyclo-decane, and some complexes of iron, cobalt, nickel, and palladium

Preparations are reported for the title ligands (L1–L4, respectively) and for [Co(L1)][ClO4]2, [Ni(L1)][ClO4]2, [{Pd(η3-C3H5)}2(L1)][ClO4]2, [Co(L2)2][ClO4]2, [Ni(L2)2][ClO4]2, [Co(L3)][ClO4]2, and [Ni(L3)2][ClO4]2. Clarification of earlier reports of L2 and some of its complexes has been achieved by X-ray crystallographic characterization. Crystal data for orthorhombic [Ni(L1)][ClO4]2: space group Pna21 (No. 33); a = 13.270(4), b = 16.564(4), c = 11.348(4) Å; Z = 4; R = 0.047, Rw = 0.040 for 1474 reflections. For monoclinic [Ni(L2)2][ClO4]2: space group P21/c (No. 14); a = 7.617(3), b = 18.034(3), c = 9.098(2) Å, β = 91.58(2)°; Z = 2; R = 0.046, Rw = 0.039 for 1487 reflections. For tetragonal [Co(L3)][ClO4]2: space group [Formula: see text] (No. 121); a = 13.840(5), c = 14.902(4) Å; Z = 4; R = 0.054, Rw = 0.058 for 974 reflections. The new complexes and previously reported [Fe(L1)][ClO4]2have been examined by cyclic voltammetry, NMR, ESR, electronic spectroscopy, and magnetic susceptibility measurements. The influence of L2's extra-cyclic hydroxyl, of changes in M—S lengths, and of O for S substitution on structural, magnetic, redox, and spectroscopic properties has been studied.