Synthesis, structural characterization, and reactivity of (thiolato)bismuth complexes as potential water-tolerant Lewis acid catalysts

We have synthesized bismuthcomplexes incorporating polydentate mono- and dithiolateligands and examined their utility as water-tolerant Lewis acid catalysts. The reaction of Bi(OAc)3 or Bi(NO3)3·5H2O and the corresponding mono- or dithiol(ate) yielded the compounds [(SNNS)Bi(OAc)] (4), [(SNNSPr)Bi(OAc)] (5), [(NNS2)Bi(OAc)] (6) and [(ONS2)Bi(OAc)] (7), [(ONS2)Bi(NO3)] (8) and [(NNS)2Bi][NO3] (9) [H2(SNNS) = N,N’-dimethyl-N,N‘-bis(2-mercaptoethyl)ethylenediamine; H2(SNNSPr) = N,N’-diethyl-N,N‘-bis(2-mercaptoethyl)propanediamine; H2(NNS2) = N,N-diethyl-N’,N‘-bis(2-mercaptoethyl)ethanediamine; H2(ONS2) = 2-methoxyethyl-bis(2-mercaptoethyl)amine; H(NNS) = N,N-diethyl-N’-(2-mercaptoethyl)ethanediamine]. The solid-state structures of 4-8 show similar distorted pentagonal pyramidalgeometries at the bismuthcentre with a thiolate sulfur atom in the axial site, while 8 shows second structural arrangement with a distorted trigonal bipyramidalgeometry at bismuth. The cation of 9 shows two NNS-bonded ligands and ...