| The coordination of the 1,4,7-trithiacyclononane (9S3), 1,5,9-trithiacyclododecane (12S3), 1,5,9,13-tetrathiacyclohexadecane (16S4), cis-3,7,11-trimethyl-1,5,9-trithiacyclododecane (cis-Me{dollar}sb3{dollar}12S3) and trans-3,7,11-trimethyl-1,5,9-trithiacyclododecane (trans-Me{dollar}sb3{dollar}12S3) polythioether macrocycles to transition metal clusters will be discussed. The reaction of 12S3 with the pentaruthenium carbide carbonyl cluster Ru{dollar}rmsb5(CO)sb{lcub}15{rcub}(musb5{dollar}-C) produced two new compounds, {dollar}rm Rusb5(CO)sb{lcub}13{rcub}(mu{dollar}-{dollar}etasp1{dollar}-12S3)({dollar}musb5{dollar}-C) and {dollar}rm Rusb5(CO)sb{lcub}11{rcub}(mu{dollar}-{dollar}etasp3{dollar}-12S3)({dollar}musb5{dollar}-C). The reaction of 12S3 and 16S4 with the hexaruthenium carbide carbonyl cluster {dollar}rm Rusb6(CO)sb{lcub}17{rcub}(musb6{dollar}-C) produced two new compounds, {dollar}rm Rusb6(CO)sb{lcub}13{rcub}(mu{dollar}-{dollar}etasp3{dollar}-12S3)({dollar}musb6{dollar}-C) and {dollar}rm Rusb6(CO)sb{lcub}15{rcub}(mu{dollar}-{dollar}etasp2{dollar}-16S4)({dollar}musb6{dollar}-C) respectively. The reaction of 9S3 with {dollar}rm Rusb6(CO)sb{lcub}17{rcub}(musb6{dollar}-C) produced two new compounds, {dollar}rm Rusb6(CO)sb{lcub}14{rcub}(etasp3{dollar}-9S3)({dollar}musb6{dollar}-C) and {dollar}rm Rusb6(CO)sb{lcub}14{rcub}(musb3{dollar}-{dollar}eta sp3{dollar}-SCH{dollar}rmsb2CHsb2SCHsb2CHsb2S)(musb5{dollar}-C). Sulfur's preference for the coinage metals was demonstrated with the extraction of copper by 12S3 from the mixed metal cluster {dollar}rm Cusb2Rusb6(CO)sb{lcub}16{rcub}(musb6{dollar}-C)(NCMe){dollar}sb2{dollar} which produced the new compound {dollar}rmlbrack Cu(etasp3{dollar}-12S3)({dollar}etasp1{dollar}-12S3)) {dollar}rmsb2lbrack Rusb6(CO)sb{lcub}16{rcub}(musb6{dollar}-C)). The reaction of cis-Me312S3 and trans-Me312S3 with {dollar}rm Rusb6(CO)sb{lcub}17{rcub}(musb6{dollar}-C) produced the new compounds {dollar}rm Rusb6(CO)sb{lcub}13{rcub}(mu{dollar}-{dollar}etasp3{dollar}-cis-Me{dollar}sb3{dollar}12S3)({dollar}musb6{dollar}-C) and {dollar}rm Rusb6(CO)sb{lcub}13{rcub}(mu{dollar}-{dollar}etasp3{dollar}-trans-Me{dollar}sb3{dollar}12S3)({dollar}musb6{dollar}-C), respectively.; A new catalytic route to polyselenoether macrocycles was discovered. It involves the catalytic cyclooligomerization of 3,3-dimethylselenatane (DMSe) by dirhenium carbonyl clusters and produced three new polyselenoether macrocycles, 3,3,7,7-tetramethyl-1,5-diselenacyclooctane (Me{dollar}sb4{dollar}8Se2), 3,3,7,7,11,11-hexamethyl-1,5,9-triselenacyclododecane, (Me{dollar}sb6{dollar}12Se3), 3,3,7,7,11,11,15,15-octamethyl-1,5,9,13-tetraselenacyclohexadecane, (Me{dollar}sb8{dollar}16Se4). Two complexes of Me{dollar}sb6{dollar}12Se3, Re{dollar}rmsb2(CO)sb9(Mesb6{dollar}12Se3) and Cu{dollar}rmsb4Isb4(mu{dollar}-Me{dollar}rmsb612Se3)sb2{dollar} were obtained from the reactions with Re{dollar}rmsb2(CO)sb9{dollar}(NCMe) and CuI, respectively. |
