Photoelectron spectroscopy of f-element organometallic complexes. 12. A comparative investigation of the electronic structure of lanthanide bis(polymethylcyclopentadienyl)hydrocarbyl complexes by relativistic ab initio and DV-Xα calculations and gas-phase UV photoelectron spectroscopy

Santo Di Bella, Antonino Gulino, Giuseppe Lanza, Ignazio Fragalà, David Stern, Tobin J Marks

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Abstract

The electronic structure of the bis(polymethylcyclopentadienyl)lanthanide hydrocarbyl complexes Cp′2LnCH(SiMe3)2 and Me2SiCp″2LnCH(SiMe3)2 (Cp′ = η5-(CH3)5C5; Cp″ = η5-(CH3)4C5; Ln = La, Ce, Nd, Sm, Lu) is investigated by means of relativistic effective core potential ab initio and discrete variational Xα calculations and by experimental gas-phase He I/He II photoelectron spectroscopic measurements. The lanthanide-ligand bonding is dominated by interactions involving the metal 5d subshells, while metal 4f orbitals are only marginally involved in the bonding. Good agreement between experimental and calculated ionization energies is found in the case of the lanthanum complex. Metal f-1 ionizations, observed in the He II spectra of the Ln = Ce, Nd, Sm, and Lu complexes, are interpreted on the basis of the ion states generated upon ionization of the corresponding fn ground states and are consistent with a gradual energetic stabilization of 4f orbitals across the lanthanide series. Analysis of the photoelectron data indicates pronounced similarity in the lanthanide-ligand bonding on traversing the lanthanide series.

Original languageEnglish
Pages (from-to)3810-3815
Number of pages6
JournalOrganometallics
Volume13
Issue number10
Publication statusPublished - 1994

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Lanthanoid Series Elements
Organometallics
Photoelectron spectroscopy
Ultraviolet spectroscopy
Electronic structure
Gases
photoelectron spectroscopy
vapor phases
electronic structure
ionization
photoelectrons
metals
Metals
orbitals
Photoelectrons
ligands
Ionization
lanthanum
Ligands
Lanthanum

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

@article{40898ef9780349c48ef878bd5aa3178d,
title = "Photoelectron spectroscopy of f-element organometallic complexes. 12. A comparative investigation of the electronic structure of lanthanide bis(polymethylcyclopentadienyl)hydrocarbyl complexes by relativistic ab initio and DV-Xα calculations and gas-phase UV photoelectron spectroscopy",
abstract = "The electronic structure of the bis(polymethylcyclopentadienyl)lanthanide hydrocarbyl complexes Cp′2LnCH(SiMe3)2 and Me2SiCp″2LnCH(SiMe3)2 (Cp′ = η5-(CH3)5C5; Cp″ = η5-(CH3)4C5; Ln = La, Ce, Nd, Sm, Lu) is investigated by means of relativistic effective core potential ab initio and discrete variational Xα calculations and by experimental gas-phase He I/He II photoelectron spectroscopic measurements. The lanthanide-ligand bonding is dominated by interactions involving the metal 5d subshells, while metal 4f orbitals are only marginally involved in the bonding. Good agreement between experimental and calculated ionization energies is found in the case of the lanthanum complex. Metal f-1 ionizations, observed in the He II spectra of the Ln = Ce, Nd, Sm, and Lu complexes, are interpreted on the basis of the ion states generated upon ionization of the corresponding fn ground states and are consistent with a gradual energetic stabilization of 4f orbitals across the lanthanide series. Analysis of the photoelectron data indicates pronounced similarity in the lanthanide-ligand bonding on traversing the lanthanide series.",
author = "{Di Bella}, Santo and Antonino Gulino and Giuseppe Lanza and Ignazio Fragal{\`a} and David Stern and Marks, {Tobin J}",
year = "1994",
language = "English",
volume = "13",
pages = "3810--3815",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
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TY - JOUR

T1 - Photoelectron spectroscopy of f-element organometallic complexes. 12. A comparative investigation of the electronic structure of lanthanide bis(polymethylcyclopentadienyl)hydrocarbyl complexes by relativistic ab initio and DV-Xα calculations and gas-phase UV photoelectron spectroscopy

AU - Di Bella, Santo

AU - Gulino, Antonino

AU - Lanza, Giuseppe

AU - Fragalà, Ignazio

AU - Stern, David

AU - Marks, Tobin J

PY - 1994

Y1 - 1994

N2 - The electronic structure of the bis(polymethylcyclopentadienyl)lanthanide hydrocarbyl complexes Cp′2LnCH(SiMe3)2 and Me2SiCp″2LnCH(SiMe3)2 (Cp′ = η5-(CH3)5C5; Cp″ = η5-(CH3)4C5; Ln = La, Ce, Nd, Sm, Lu) is investigated by means of relativistic effective core potential ab initio and discrete variational Xα calculations and by experimental gas-phase He I/He II photoelectron spectroscopic measurements. The lanthanide-ligand bonding is dominated by interactions involving the metal 5d subshells, while metal 4f orbitals are only marginally involved in the bonding. Good agreement between experimental and calculated ionization energies is found in the case of the lanthanum complex. Metal f-1 ionizations, observed in the He II spectra of the Ln = Ce, Nd, Sm, and Lu complexes, are interpreted on the basis of the ion states generated upon ionization of the corresponding fn ground states and are consistent with a gradual energetic stabilization of 4f orbitals across the lanthanide series. Analysis of the photoelectron data indicates pronounced similarity in the lanthanide-ligand bonding on traversing the lanthanide series.

AB - The electronic structure of the bis(polymethylcyclopentadienyl)lanthanide hydrocarbyl complexes Cp′2LnCH(SiMe3)2 and Me2SiCp″2LnCH(SiMe3)2 (Cp′ = η5-(CH3)5C5; Cp″ = η5-(CH3)4C5; Ln = La, Ce, Nd, Sm, Lu) is investigated by means of relativistic effective core potential ab initio and discrete variational Xα calculations and by experimental gas-phase He I/He II photoelectron spectroscopic measurements. The lanthanide-ligand bonding is dominated by interactions involving the metal 5d subshells, while metal 4f orbitals are only marginally involved in the bonding. Good agreement between experimental and calculated ionization energies is found in the case of the lanthanum complex. Metal f-1 ionizations, observed in the He II spectra of the Ln = Ce, Nd, Sm, and Lu complexes, are interpreted on the basis of the ion states generated upon ionization of the corresponding fn ground states and are consistent with a gradual energetic stabilization of 4f orbitals across the lanthanide series. Analysis of the photoelectron data indicates pronounced similarity in the lanthanide-ligand bonding on traversing the lanthanide series.

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