Supramolecular assemblies of tungsten complexes with unusual chelating groups

Timothy E. Baroni, Vladimir Kolesnichenko, Lawrence Seib, Joseph A. Heppert, Louise M. Liable-Sands, Glenn P.A. Yap, Arnold E. Rheingold

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Abstract

Metal complexes of ligands with η1-O coordinated carbonyl moieties are well-known throughout the inorganic literature. However, metal complexes containing authentic acid chloride ligands have not previously been isolated. The synthesis and characterization of compounds with the formula W(X)Cl3(OPh-2-COCl) (2) [X = O (2a), NC6H3-2,6-(CH3)2 (2b), and Ph2C2 (2c)] are reported. The crystal structures of 2a and 2c were solved, showing the interaction of the acid chloride carbonyl moiety with the tungsten center. Complex 2c adopts a channelled structure having six-fold symmetric voids in the solid state. As was anticipated, the coordinated acid chloride of 2a reacts readily with nucleophiles to produce the ester WOCl3(OPh-2-COPrn) (3) and the amide WOCl3(OPh-2-CONHBut) (4a). A related amide complex WOCl3(OPh-2-CONH2) (4b), synthesized by the reaction of WOCl4 with salicylamide, displays an infinite-chain structure supported by hydrogen bonding between the amide group and the oxo ligand of an adjacent tungsten complex. The η1-O coordinated nitro compounds W(X)Cl3(OPh-2-NO2) (5) [X = O (5a), NC6H3-2,6-(CH3)2 (5b), and Ph2C2 (5c)] have also been isolated and the crystal structure of 5c is reported.

Original languageEnglish
Pages (from-to)759-768
Number of pages10
JournalPolyhedron
Volume17
Issue number5-6
DOIs
StatePublished - 1998

Keywords

  • Acid chloride
  • Hydrogen bonding
  • Materials
  • Salicylate
  • Tungsten

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    Baroni, T. E., Kolesnichenko, V., Seib, L., Heppert, J. A., Liable-Sands, L. M., Yap, G. P. A., & Rheingold, A. E. (1998). Supramolecular assemblies of tungsten complexes with unusual chelating groups. Polyhedron, 17(5-6), 759-768. https://doi.org/10.1016/S0277-5387(97)00313-6