Thiophenophane metal complexes. II. Preparation, structure, and properties of binuclear copper(II) complexes and of 2,5,9,12-tetrathia[13](2,5) thiophenophane. Evidence for <i>S</i>-coordinated thiophene

Abstract

Preparations of the thiophenophane C 13 H 20 S 5 , (L2), its binuclear copper(II) complex, (CuCl 2 •L2) 2 and the related thiophenophane complex (CuCl 2 •L1) 2 (L1 = C 10 H 14 S 4 ) are described. The 13 C and 1 H nmr spectra of L2 and the ir and electronic spectra of the complexes are reported. The molecular structures of L2, (CuCl 2 •L1) 2 , and (CuCl 2 •L2) 2 have been determined. For L2: space groupP2 1 /a,a = 14.658(1), b = 5.9800(3), c = 19.772(2) Å, β = 111.00(1)°, Z = 4, R f = 0.050,R w = 0.046. For (CuCl 2 •L1) 2 : space group Pbca, a = 15.383(6), b = 11.409(3), c = 17.423(4) Å, Z = 4, R f = 0.057, R w = 0.036. For (CuCl 2 •L2) 2 : space group A 2 /a, a = 12.616(1), b = 10.0542(6), c = 29.180(2) Å, β = 95.81(1)°, Z = 4, R f = 0.055, R w = 0.038. The complex (CuCl 2 •L1) 2 has distorted octahedral coordination geometry about each copper. The copper atoms are linked by two bridging chlorines and each copper also bears one terminal chlorine, two thioether-sulfurs and a thiophene-sulfur. In contrast, (CuCl 2 •L2) 2 does not involve coordination by thiophene-sulfur and the remaining coordination sphere has undergone distortion from square pyramidal towards trigonal bipyramidal. Differences in the electronic spectra are interpreted in terms of the structures of the complexes. Keywords: binuclear copper(II) thiophenophane complex.