THIOPHENOPHANE METAL-COMPLEXES .1. PREPARATION, X-RAY STRUCTURE, AND CYCLIC VOLTAMMETRY OF 2,5,8-TRITHIA[9](2,5)THIOPHENOPHANE, L, AND OF ITS METAL-COMPLEX CATION BIS(2,5,8-TRITHIA[9](2,5)THIOPHENOPHANE-S2,S3]COPPER(I),[CUL2]+

Preparation of the thiophenophanc C10H14S4, (L), and syntheses of its copper(I) complex [CuL2]Cl4 or (CuL2liBF4 are described. The 53C and H nmr spectra of L and the ir spectra (4000-200 cm) of [CuL2]C104 and [CuL2]BF4 are reported. The molecular structures of L and [CuL2]C104 have been determined. For L: space group P2a, a = 7.9347(2) A, b = 18.7479(3) A, c = 8.8596(2) A, 0 = 108.446(2)°, Z = 4, f=0.048, and Rw = 0.034. For [CuL2]C104: space group P21c, a = 9.4363(1) A, b = 18.2768(3) A, c = 16.2157(3) A, = 96.520(2)°, Z = 4, Rf = 0.056, and Rw = 0.037. The Cu(I) complex has distorted tetrahedral coordination geometry; its perchlorate anion is non-coordinating and disordered. The Cu-S bond lengths lie in the range 2.301-2.392 A and the S-Cu-S angles in Ihe range 92.43-150.26°. Cyclic voltammetry of [CuL2]C104 (10-3 mol/L in dimethylsulfoxide, 0.1 mol/L Et4NC104, glassy carbon working electrode, platinum counter electrode, aqueous saturated calomel reference electrode against which the ferrocenium/ferrocene potential under similar conditions was 400 mV) shows a quasi-reversible oxidation (Ev2 = 0.150 V, £p = 170 mV at 50 mV/s). Thiophene's effect as a sub-unit in a small macrocycle upon properties of the latter is discussed. © 1988 Canadian Science Publishing. All rights reserved.