Photoelectron spectroscopy of f-element organometallic complexes. 10. Investigation of the electronic structure and geometry of bis(η5-pentamethylcyclopentadienyl)phosphathoracyclobutane by relativistic ab initio, multipolar DV-Xa calculations and gas-phase UV photoelectron spectroscopy

Santo Di Bella, Antonino Gulino, Giuseppe Lanza, Ignazio L. Fragalà, Tobin J Marks

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The electronic structure of the phosphathoracyclobutane Cp′2Th(CH2PMeCH2) complex (Cp′ = η5-Me5C5) has been investigated by a combination of ab initio relativistic effective core potential calculations for geometry optimization, DV-Xα calculations, and UV photoelectron spectroscopy. The formation of the four-membered ring involves bonding interactions analogous to those found in cyclobutane. Metal-ligand bonding involves both 5f and 6d metal atomic orbitals with a major role of the latter. The gas-phase UV photoelectron spectrum has been assigned using both comparative arguments and TSIE values obtained from DV-Xα calculations, as well as PE data on the closely related Cp′2Th(CH2SiMe2CH2) complex. The optimized structure is indicative of a slightly puckered four-membered metallacyclic ring having the P-CH3 vector in an endocyclic axial orientation. The structure shows close analogies with diffraction data for the related Cp′2Th(CH2SiMe2CH2) complex. According with NMR data, a single energy minimum has been found for the conformation with smaller intraligand repulsive interactions involving the P3p lone pair.

Original languageEnglish
Pages (from-to)3326-3332
Number of pages7
Issue number8
Publication statusPublished - 1993


ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

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