Unsaturated thiacrown ethers: synthesis, physical properties, and formation of a silver complex.

TLDR: The cyclic voltammograms of 4-8 indicate that the larger unsaturated thiacrown ethers were oxidized more easily than the smaller systems, and unsaturated dichloroethylene with sodium sulfide systems were oxidationized more quickly than corresponding saturated systems.

Abstract: The 6-, 9-, 12-, 15-, 18-, 21-, 24-, and 27-membered unsaturated thiacrown ethers 1−8 were formed by reaction of cis-1,2-dichloroethylene with sodium sulfide in acetonitrile. Crystal structures of 4−8 were determined by X-ray crystallography, and it was found that all sulfur atoms of 5−8 direct to the inside of the ring (endodentate). All of the ORTEP drawings show that there are cavities in these molecules, and the cavity sizes in 4−8 were 1.76, 2.34, 3.48, 4.43, and 5.36 A, respectively. The UV spectra of 4−8 showed absorption maximums at the range of 255−276 nm in acetonitrile, and the absorption maximums of 4−8 were found to shift to longer wavelengths by changing the solvent from acetonitrile to cyclohexane. The cyclic voltammograms of 4−8 indicate that the larger unsaturated thiacrown ethers were oxidized more easily than the smaller systems, and unsaturated thiacrown ethers were oxidized more easily than corresponding saturated systems. The reaction of 4 with silver trifluoroacetate in acetone affo...