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 Citations (Scopus)

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

Fingerprint

Organometallics
assemblies
Hydrogen bonds
acids
Acids
Salicylates
salicylates
Chelation
Phenol
hydrogen bonds
phenols
Oxygen
Ligands
Acetylene
Tungsten
Molecules
Salicylic Acid
Dimerization
solid state
ligands

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

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

Supramolecular assemblies involving organometallic free acids. / Baroni, Timothy E.; Heppert, Joseph A.; Hodel, Rolande R.; Kingsborough, Richard P.; Morton, Martha D; Rheingold, Arnold L.; Yap, Glenn P.A.

In: Organometallics, Vol. 15, No. 22, 29.10.1996, p. 4872-4879.

Research output: Contribution to journalArticle

Baroni, TE, Heppert, JA, Hodel, RR, Kingsborough, RP, Morton, MD, Rheingold, AL & Yap, GPA 1996, 'Supramolecular assemblies involving organometallic free acids', Organometallics, vol. 15, no. 22, pp. 4872-4879. https://doi.org/10.1021/om960361g
Baroni TE, Heppert JA, Hodel RR, Kingsborough RP, Morton MD, Rheingold AL et al. Supramolecular assemblies involving organometallic free acids. Organometallics. 1996 Oct 29;15(22):4872-4879. https://doi.org/10.1021/om960361g
Baroni, Timothy E. ; Heppert, Joseph A. ; Hodel, Rolande R. ; Kingsborough, Richard P. ; Morton, Martha D ; Rheingold, Arnold L. ; Yap, Glenn P.A. / Supramolecular assemblies involving organometallic free acids. In: Organometallics. 1996 ; Vol. 15, No. 22. pp. 4872-4879.
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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 {\AA} 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.",
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