Electronic Structure of the d1 Bent-metallocene Cp2VCl2: A Photoelectron and Density Functional Study

摘要

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.