Synthesis of trithiolanes and tetrathianes from thiiranes catalyzed by ruthenium salen nitrosyl complexes.
The compound [Ru(salen)(NO)(H(2)O)](SbF(6)) (1) (salen = N,N'-ethylene-bis-salicylidene aminate) reacts catalytically with thiiranes and converts them to olefins and 1,2,3,4-tetrathianes or 1,2,3-trithiolanes. The monosubstituted thiiranes styrene sulfide and propylene sulfide reacted to form the corresponding olefin and the 4-substituted 1,2,3-trithiolane in a 2:1 ratio in isolated yields in excess of 90%. The disubstituted thiirane cis-stilbene sulfide was converted to cis-stilbene and 5,6-trans-1,2,3,4-diphenyltetrathiane in a 3:1 ratio in the presence of a catalytic amount of 1 in CD(3)NO(2). Coordination of cis-stilbene sulfide to the salen complex in a ligand substitution reaction was established by isolation of [Ru(salen)(NO)(cis-stilbene sulfide)](SbF(6)) (6). (1)H NMR studies performed on 6 indicated that the salen macrocycle had rearranged upon thiirane coordination. A similar rearrangement was found to be stabilized by other ligands including tetramethylethylene sulfide, tetrahydrothiophene, and d(3)-acetonitrile. The alpha-deuterio-cis-stilbene sulfide catalyst adduct (d-6) reacted with unlabeled cis-stilbene sulfide to form deuterium-labeled trans-diphenyl-tetrathiane and unlabeled cis-stilbene as shown by GCMS and (1)H NMR. Thus, the solution thiirane behaves as a sulfur donor and forms olefin, whereas the coordinated thiirane becomes the cyclic polysulfide. beta-cis-Deuteriostyrene sulfide was used to show that ring closure to form cyclic polysulfide incorporated inversion of stereochemistry versus starting thiirane. A mechanism for catalysis consistent with experimental data is presented that requires coordination of thiirane to the metal complex followed by bimolecular attack of free thiirane on the coordinated thiirane.
Sauve
Anthony A
AA
Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA.
Groves
John T
JT