The synthesis and structure of bis(1,4,7-trithiacyclodecane)-ruthenium (II) perchlorate: the meso diastereoisomer

Abstract

The synthesis of the Ru(II) crown thioether complex, bis(1,4,7-trithiacyclodecane) ruthenium (II) perchlorate, [Ru(10S3)2](ClO4)2, and a study of its properties utilizing single crystal X-ray diffraction, electronic spectroscopy, 13C NMR spectroscopy and cyclic voltammetry is reported. The crystal structure shows the two 10S3 ligands are arranged in a trans or anti fashion around the ruthenium (II) center in nearly octahedral fashion to yield the meso stereoisomer. 13C NMR spectroscopy demonstrates that this stereoisomer is also the predominant one observed in solution, in contrast to the Co(III) and Fe(II) complexes. The electronic absorption spectrum is similar to other previously observed hexakis (thioether) ruthenium (II) complexes with d-d transitions at 346 and 297 nm. The electrochemical behavior is also similar to related Ru(II) complexes and shows a single quasi-reversible oxidation wave at + 1.37 V versus Fc/Fc+. Crystal data for [Ru(10S3)2](ClO4)2: C14H28Cl2O8RuS6; monoclinic, space group P21/c; a = 7.391(2), b = 9.480(2), c = 17.351(3) A; β = 97.10(2)0, V = 1206.4(5) A3; Z = 2; R = 0.0521; D = 1.896 g cm−3; 3211 reflections measured. The properties of the complex are compared with the congeneric Fe complex.