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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6 Citations (Scopus)

Abstract

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
JournalOrganometallics
Volume12
Issue number8
Publication statusPublished - 1993

Fingerprint

Organometallics
Photoelectron spectroscopy
Ultraviolet spectroscopy
Electronic structure
Gases
photoelectron spectroscopy
vapor phases
electronic structure
Geometry
geometry
Metals
Cyclobutanes
cyclobutane
rings
Photoelectrons
metals
Conformations
photoelectrons
Diffraction
Nuclear magnetic resonance

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

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title = "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",
abstract = "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.",
author = "{Di Bella}, Santo and Antonino Gulino and Giuseppe Lanza and Fragal{\`a}, {Ignazio L.} and Marks, {Tobin J}",
year = "1993",
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pages = "3326--3332",
journal = "Organometallics",
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TY - JOUR

T1 - 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

AU - Di Bella, Santo

AU - Gulino, Antonino

AU - Lanza, Giuseppe

AU - Fragalà, Ignazio L.

AU - Marks, Tobin J

PY - 1993

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N2 - 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.

AB - 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.

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