Bismuth-substituted "sandwich" type polyoxometalate catalyst for activation of peroxide: Umpolung of the peroxo intermediate and change of chemoselectivity

Srinivasa Rao Amanchi, Alexander M. Khenkin, Yael Diskin-Posner, Ronny Neumann

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

The epoxidation of alkenes with peroxides by WVI, MoVI, VV, and TiIV compounds is well established, and it is well accepted that the active intermediate peroxo species are electrophilic toward nucleophilic substrates. Polyoxotungstates, for example, those of the "sandwich" structure, [WZn(TM-L)2(ZnW9O34)2]q- in which TM = transition metal and L = H2O, have in the past been found to be excellent epoxidation catalysts. It has now been found that substituting the Lewis basic BiIII into the terminal position of the "sandwich" polyoxometalate structure to yield [Zn2BiIII2(ZnW9O34)2]14- leads to an apparent umpolung of the peroxo species and formation of a nucleophilic peroxo intermediate. There are two lines of evidence that support the formation of a reactive nucleophilic peroxo intermediate: (1) More electrophilic sulfoxides are more reactive than more nucleophilic sulfides, and (2) nonfunctionalized aliphatic alkenes and dienes showed ene type reactivity rather than epoxidation pointing toward "dark" formation of singlet oxygen from the nucleophilic intermediate peroxo species. Allylic alcohols reacted much faster than alkenes but showed chemoselectivity toward C-H bond activation of the alcohol and formation of aldehydes or ketones rather than epoxidation. This explained via alkoxide formation at the BiIII center followed by oxidative β-elimination.

Original languageEnglish
Pages (from-to)3336-3341
Number of pages6
JournalACS Catalysis
Volume5
Issue number6
DOIs
Publication statusPublished - Jun 5 2015

    Fingerprint

Keywords

  • bismuth
  • homogeneous catalysis
  • peroxide
  • polyoxometalate
  • singlet oxygen

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this