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. 2008 Apr 15;693(8-9):1621-1627.
doi: 10.1016/j.jorganchem.2007.12.035.

Electronic Structure of the d Bent-metallocene Cp(2)VCl(2): A Photoelectron and Density Functional Study

Matthew A Cranswick  1 , Nadine E Gruhn, John H Enemark, Dennis L Lichtenberger
Affiliations

Electronic Structure of the d Bent-metallocene Cp(2)VCl(2): A Photoelectron and Density Functional Study

Matthew A Cranswick et al. J Organomet Chem. .

Abstract

The Cp(2)VCl(2) 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 Cp(2)VCl. With improved instrumentation, the amount of decomposition is reduced and subtraction of ionization intensity due to Cp(2)VCl from the Cp(2)VCl(2)/Cp(2)VCl mixed spectrum yields the Cp(2)VCl(2) 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 d(1) electron and the energies of the higher positive ion states of Cp(2)VCl(2). The calculations also account well for the trends to the other Group V bent metallocene dichlorides Cp(2)NbCl(2) and Cp(2)TaCl(2). The first ionization energy of Cp(2)VCl(2) is considerably greater than the first ionization energies of the second- and third-row transition metal analogues.

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Figures

Figure 1
Figure 1
Low energy He I spectra showing the extraction of the Cp2VCl2 spectrum from the data: (A) spectrum of Cp2VCl, (B) spectrum of Cp2VCl2 sample loaded directly into ionization chamber, (C) spectrum of Cp2VCl2 sample effused directly into photon beam from a quartz crucible, (D) subtraction of A from C to give difference Cp2VCl2 spectrum.
Figure 2
Figure 2
He I photoelectron spectra of Cp2VCl2, Cp2NbCl2 and Cp2TaCl2.
Figure 3
Figure 3
Spin correlation diagram for Cp2VCl2 showing α- and β-spin molecular orbital character and electron occupations.
See this image and copyright information in PMC

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