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

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.

Interaction of metallocene dichlorides with apo-human transferrin: A spectroscopic study and cytotoxic activity against human cancer cell lines

“…Some early and late transition metals (highlighted in yellow color) are known (A) to form Cp 2 M(IV)Cl 2 and cisplatin, respectively. General representation of the molecular structure of a metallocene dichloride (B), where the angle M (Cl-M-Cl) =Ti +4 (94.6°), 37 V +4 (87.1°), 38 Mo +4 (81.3°/82.0°), 39,40 Nb +4 (85.7°), 39 Zr +4 (97.2°), 39 W +4 (81.5°) 41 and Hf +4 (98.0°). 40 The molecular structure of cisplatin (C),where the Cl-Pt-Cl angle is 91.9°.…”