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Unsaturated Thiacrown Ethers:  Synthesis, Physical Properties, and Formation of a Silver Complex

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journal contribution
posted on 2001-10-27, 00:00 authored by Takahiro Tsuchiya, Toshio Shimizu, Nobumasa Kamigata
The 6-, 9-, 12-, 15-, 18-, 21-, 24-, and 27-membered unsaturated thiacrown ethers 18 were formed by reaction of cis-1,2-dichloroethylene with sodium sulfide in acetonitrile. Crystal structures of 48 were determined by X-ray crystallography, and it was found that all sulfur atoms of 58 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 48 were 1.76, 2.34, 3.48, 4.43, and 5.36 Å, respectively. The UV spectra of 48 showed absorption maximums at the range of 255−276 nm in acetonitrile, and the absorption maximums of 48 were found to shift to longer wavelengths by changing the solvent from acetonitrile to cyclohexane. The cyclic voltammograms of 48 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 afforded the colorless complex AgI(C2H2S)5(CF3COO) 9. The crystal structure of 9 was determined by X-ray analysis, and it was found that three of the five sulfur atoms bonded to the silver atom.