| The reaction between WCl{dollar}sb4{dollar} and an excess of thioether (L) under refluxing and reducing conditions produced a mixture of Cl{dollar}sb3{dollar}W({dollar}mu{dollar}-L){dollar}sb3{dollar}WCl{dollar}sb3{dollar} (L = 1,4-dithiane 12, 1,4-thioxane 13, pms 7) and (X) (Cl{dollar}sb3{dollar}W({dollar}mu{dollar}-L){dollar}sb2{dollar}({dollar}mu{dollar}-Cl)WCl{dollar}sb3{dollar}) (L = 1,4-dithiane 14, 1,4-thioxane 15, pms 8 for X = Na; L = 1,4-dithiane 16, 1,4-thioxane 17 for X = PPh{dollar}sb4{dollar}). X-ray crystallographic analyses of 12, 13, 7, 16 and 17 revealed they possess confacial bioctahedral frameworks. The type of thioether was observed to affect product distribution. Reversible one electron reductions occurred for 12, 13, 16, 17, and (X) (Cl{dollar}sb3{dollar}W({dollar}mu{dollar}-tht){dollar}sb2{dollar}({dollar}mu{dollar}-Cl)WCl{dollar}sb3{dollar}) X = Na 20; X = PPh{dollar}sb4{dollar} 21).; 12, 13, 7 and Cl{dollar}sb3{dollar}W({dollar}mu{dollar}-tht){dollar}sb3{dollar}WCl{dollar}sb3{dollar} 1 reacted with one equivalent of a monoanionic nucleophile to ring-open a bridging thioether, producing potential lariat metallo-containing ligands. The crystal structure of (PPN) (Cl{dollar}sb3{dollar}W({dollar}mu{dollar}-tht){dollar}sb2(mu{dollar}-S(CH{dollar}sb4{dollar})Sptol)WCl{dollar}sb3{dollar}) 3 has been solved and indicates retention of a stable WS{dollar}sb3{dollar}W core. Reaction of ring-opened complexes with late transition metal centres has led to complexation. X-ray crystallographic analyses of (Ag) (Cl{dollar}sb3{dollar}W({dollar}mu{dollar}-L){dollar}sb2{dollar}({dollar}mu{dollar}-S(CH{dollar} sb2)sb2{dollar}E(CH{dollar}sb2)sb2{dollar}SC{dollar}sb6{dollar}H{dollar}sb4{dollar}(o-PPh{dollar}sb2{dollar})WCl{dollar}sb3{dollar}) (L = tht, E = no atoms 81; L = 1,4-thioxane, E = O 83; L = pms, E = CH{dollar}sb2{dollar} 84) justified the use of the term lariat metalloligand.; Cl{dollar}sb3{dollar}W({dollar}mu{dollar}-tht){dollar}sb3{dollar}WCl{dollar}sb3{dollar} 1 reacted with two equivalents of the monoanionic nucleophile RS{dollar}sp-{dollar} (R = ptol, Et, SC{dollar}sb6{dollar}H{dollar}sb4{dollar}(o-PPh{dollar}sb2{dollar})) to produce (Cl{dollar}sb3{dollar}W({dollar}mu{dollar}-tht)({dollar}mu{dollar}-S(CH{dollar}sb4{dollar})SR){dollar}sb2{dollar}WCl{dollar}sb 3{dollar}) {dollar}sp{lcub}2-{rcub}.{dollar} NMR data indicated that during complexation to late transition metal centres several different modes of coordination were being adopted.; Ring-opening using dianionic metallo-based anions (e.g. WS{dollar}sb4sp{lcub}2-{rcub}){dollar} produced highly unstable complexes. The metallo-based anion HFe(CO){dollar}sb4sp-{dollar} functioned as a hydride.; Polyether-based dianions with alkyl backbones open one thioether ring to produce products that are prone to degradation of the pendant arm through neighbouring group effects. Polyether-based dianions with aromatic backbones produce lariat, pseudo-lariat and suspected macrocyclic metalloligands. The latter two metalloligands bind the later transition-metals, forming extended structures or discrete complexes, by adopting a number of coordination modes. |
