"Small Iron-Carbonyl Clusters Bearing Imidazolium-2-trithioperoxycarboxylate Ligands"

Tomás F. Beltrán, Guillermo Zaragoza, and Lionel Delaude

Journal Cover 
          source: Dalton Transactions
            year: 2017
          volume: 46
      first page: 13002
       last page: 13009
             doi: 10.1039/c7dt03202a
graphical abstract

Abstract: The reaction of [Fe2(CO)9] with two representative imidazolium-2-dithiocarboxylate zwitterions derived from common N-heterocyclic carbenes (NHCs) bearing mesityl (IMes) or 2,6-diisopropylphenyl substituents on their nitrogen atoms (IDip) unexpectedly afforded two small bimetallic iron-carbonyl clusters with the generic formula [Fe2(CO)6(μ-κ2-S,S'-κ2-S,S'-S3C·NHC)]. After a brief optimization of the reaction conditions, these two “sulfur-enriched” products were isolated in low yields. They were fully characterized by IR, NMR, UV/Visible, and ESI-MS techniques, and their molecular structures were determined by single crystal X-ray diffraction analysis. The two compounds adopted a butterfly-type disposition in the solid state, with an [Fe2(CO)6] core bridged by the trithioperoxycarboxylate moiety of the in situ generated NHC·CS3 ligands. Bond lengths recorded for the CS3- unit revealed that its negative charge was mostly located on the remote sulfur atom.

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