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 language | English |
|---|---|
| Pages (from-to) | 3810-3815 |
| Number of pages | 6 |
| Journal | Organometallics |
| Volume | 13 |
| Issue number | 10 |
| Publication status | Published - 1994 |
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ASJC Scopus subject areas
- Inorganic Chemistry
- Organic Chemistry
Cite this
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. / Di Bella, Santo; Gulino, Antonino; Lanza, Giuseppe; Fragalà, Ignazio; Stern, David; Marks, Tobin J.
In: Organometallics, Vol. 13, No. 10, 1994, p. 3810-3815.Research output: Contribution to journal › Article
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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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M3 - Article
AN - SCOPUS:0007330390
VL - 13
SP - 3810
EP - 3815
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 10
ER -