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A rationale for the linear correlation of aryl substituent effects in iron(0) tricarbonyl complexes containing alpha,beta-unsaturated enone (chalcone) ligands

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JournalOrganometallics
DatePublished - 3 Dec 2007
Issue number25
Volume26
Number of pages12
Pages (from-to)6354-6365
Original languageEnglish

Abstract

A library of iron(0) tricarbonyl complexes containing eta(4) -bound alpha,beta-unsaturated enone ligands [Fe-(CO3(eta(4)-RCH=CH-C{Ph}=O)] has been prepared to facilitate comprehensive correlation of the electronic withdrawing/donating properties of the substituent, R, with the strength of the metal-ligand interaction. The IR and NMR spectroscopic data proved invaluable in aiding a comprehensive correlation and global understanding of the aryl substituent effects. The frequency of the M-CO bands in the infrared spectra of these species exhibits a linear correlation with the Hammett parameters for the substituents. The coordination shifts in both the H-1 and C-13 NMR spectra for the ligands exhibit a similar linear relationship. The largest coordination shifts are observed when more electron-withdrawing groups are present, implying that the organic ligand is primarily acting as a pi-acid. The structures of six complexes of this type have been determined by single-crystal X-ray diffraction.

    Research areas

  • TRANSITION-METAL-COMPLEXES, L = CO, ORGANIC-SYNTHESIS, (VINYLKETENE)TRICARBONYLIRON(0) COMPLEXES, TRICARBONYL(VINYLKETENE)IRON(0) COMPLEXES, BENZYLIDENEACETONEIRON TRICARBONYL, NUCLEOPHILIC-ADDITION, MAGNETIC-RESONANCE, CARBONYL-COMPLEXES, FLUXIONAL BEHAVIOR

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