Electronic structure of the d1 bent-metallocene Cp2VCl2: A photoelectron and density functional study

Matthew A. Cranswick, Nadine E. Gruhn, John H. Enemark, Dennis L Lichtenberger

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

The Cp2VCl2 molecule is a prototype for bent-metallocene complexes with a single electron in the metal d shell, but experimental measure of the binding energy of the d electron by photoelectron spectroscopy eluded early attempts due to apparent decomposition in the spectrometer to Cp2VCl. With improved instrumentation, the amount of decomposition is reduced and subtraction of ionization intensity due to Cp2VCl from the Cp2VCl2/Cp2VCl mixed spectrum yields the Cp2VCl2 spectrum exclusively. The measured ionization energies provide well-defined benchmarks for electronic structure calculations. Density functional calculations support the spectral interpretations and agree well with the ionization energy of the d1 electron and the energies of the higher positive ion states of Cp2VCl2. The calculations also account well for the trends to the other Group V bent-metallocene dichlorides Cp2NbCl2 and Cp2TaCl2. The first ionization energy of Cp2VCl2 is considerably greater than the first ionization energies of the second- and third-row transition metal analogues.

Original languageEnglish (US)
Pages (from-to)1621-1627
Number of pages7
JournalJournal of Organometallic Chemistry
Volume693
Issue number8-9
DOIs
StatePublished - Apr 15 2008

Fingerprint

Ionization potential
Photoelectrons
Electronic structure
photoelectrons
Electrons
electronic structure
ionization
Metals
Benchmarking
Photoelectron Spectroscopy
Decomposition
energy
decomposition
Photoelectron spectroscopy
Binding energy
Ions
dichlorides
Ionization
Transition metals
Density functional theory

Keywords

  • Bent-metallocenes
  • Density functional theory
  • Photoelectron spectroscopy
  • Vanadium

ASJC Scopus subject areas

  • Chemical Engineering (miscellaneous)
  • Materials Science (miscellaneous)
  • Materials Chemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Biochemistry

Cite this

Electronic structure of the d1 bent-metallocene Cp2VCl2 : A photoelectron and density functional study. / Cranswick, Matthew A.; Gruhn, Nadine E.; Enemark, John H.; Lichtenberger, Dennis L.

In: Journal of Organometallic Chemistry, Vol. 693, No. 8-9, 15.04.2008, p. 1621-1627.

Research output: Contribution to journalArticle

Cranswick, Matthew A. ; Gruhn, Nadine E. ; Enemark, John H. ; Lichtenberger, Dennis L. / Electronic structure of the d1 bent-metallocene Cp2VCl2 : A photoelectron and density functional study. In: Journal of Organometallic Chemistry. 2008 ; Vol. 693, No. 8-9. pp. 1621-1627.
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AU - Lichtenberger, Dennis L

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AB - The Cp2VCl2 molecule is a prototype for bent-metallocene complexes with a single electron in the metal d shell, but experimental measure of the binding energy of the d electron by photoelectron spectroscopy eluded early attempts due to apparent decomposition in the spectrometer to Cp2VCl. With improved instrumentation, the amount of decomposition is reduced and subtraction of ionization intensity due to Cp2VCl from the Cp2VCl2/Cp2VCl mixed spectrum yields the Cp2VCl2 spectrum exclusively. The measured ionization energies provide well-defined benchmarks for electronic structure calculations. Density functional calculations support the spectral interpretations and agree well with the ionization energy of the d1 electron and the energies of the higher positive ion states of Cp2VCl2. The calculations also account well for the trends to the other Group V bent-metallocene dichlorides Cp2NbCl2 and Cp2TaCl2. The first ionization energy of Cp2VCl2 is considerably greater than the first ionization energies of the second- and third-row transition metal analogues.

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