Preparation of Polyoxa-1,<i>n</i>-dithia[<i>n</i>](1,1′)ruthenocenophanes and the Structural Studies of Their Metal Complexes

Abstract

Abstract Polyoxa-1,n-dithia[n](1,1′)ruthenocenophanes were prepared by treatment of 1,1′-ruthenocenedithiol with α, ω-dibromo polyethers. The ruthenocenophanes formed efficiently complexes with soft ions, but not with hard and borderline cations. The 1H- and 13C-NMR spectral data of the silver(I) ion-complexed ruthenocenophanes suggested a partial electron-transfer interaction between the ruthenium atom of the ruthenocene nucleus and the incapsulated silver(I) ion. The crystal structure of the 1:1 complex of 4,7,10,13-tetraoxa-1,16-dithia[16](1,1′)ruthenocenophane with mercury(II) chloride was determined by the X-ray method. The crystals are triclinic, space group P\bar1, with a=13.722(3), b=11.678(4), c=8.179(2) Å, α=102.69(3), β=72.82(2), γ=100.73(2)°, Z=2, Dx=2.11 g cm−3. The mercury(II) cation and the two chloride ions are situated in the central cavity of the macrocyclic moiety and at the apexes, respectively. The distance between the ruthenium atom of a ruthenocene nucleus and the incapsulated mercury(II) ion is 4.846 (2) Å which is too long for direct metal–metal interaction.