Supramolecular assemblies involving organometallic free acids

Timothy E. Baroni, Joseph A. Heppert, Rolande R. Hodel, Richard P. Kingsborough, Martha D. Morton, Arnold L. Rheingold, Glenn P.A. Yap

Research output: Contribution to journalArticle

26 Scopus citations

Abstract

Reactions between W(η2-Ph2C2)Cl4 and salicylic acid derivatives generate analytically pure free acids of formula W(η2-Ph2C2)Cl3(Hsal-R) (1) in high yields (Hsal = a salicylate monoanion). The products exist as hydrogen-bonded dimers in the solid state. The acid functionality on one molecule hydrogen bonds to one of the cis-chloride ligands of an adjacent complex at a 3.03 Å distance. The more electron-rich tungsten center renders these acetylene complexes less acidic than their oxo and arylimido analogs. As a result, W(η2-Ph2C2)Cl3-(Hsal) exhibits partial dimerization in solution and have relatively weak hydrogen bonds to nitrogen- and oxygen-containing organic molecules. Among a range of possible phenol-phenoxide complexes of the W(η2-Ph2C2)Cl3 subunit, only the ether adduct of the catecholate, W(η2-Ph2C2)Cl3(Hcat-OEt 2) (2), has been isolated and structurally characterized. The weaker hydrogen bond strength of larger chelating bis(phenolates) evidently destabilize the phenol-phenoxide structures in favor of simple chelating bis(phenoxides). The salicylate free acids form various supramolecular complexes in solution and the solid state, including [W(η2-Ph2C2)Cl3(Hsal)] 4(18-Crown-6) (5), one of a family of tetranuclear systems organized around hydrogen bonding to an 18-crown-6 template. This structure is characterized by π-stacking of the Hsal ligands between confacial free acid complexes and the steric screening of the two non-hydrogen-bonded 18-crown-6 oxygens by pairs of antarafacial W(Ph2C2) units.

Original languageEnglish (US)
Pages (from-to)4872-4879
Number of pages8
JournalOrganometallics
Volume15
Issue number22
DOIs
StatePublished - Oct 29 1996

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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    Baroni, T. E., Heppert, J. A., Hodel, R. R., Kingsborough, R. P., Morton, M. D., Rheingold, A. L., & Yap, G. P. A. (1996). Supramolecular assemblies involving organometallic free acids. Organometallics, 15(22), 4872-4879. https://doi.org/10.1021/om960361g