Gv. Loukova et Vv. Strelets, Electrochemical versus optical insight in frontier orbitals of Ti(IV), Zr(IV), and Hf(IV) bent metallocenes, J ORGMET CH, 606(2), 2000, pp. 203-206
The linear relationship between the redox and optical HOMO-to-LUMO electron
transitions are reported for complex molecules with pi-ligands for the fir
st time. Linear correlations between electrochemical (redox) gaps and absor
ption charge-transfer energies have been noted for Ti(IV), Zr(IV), and Hf(I
V) bis(cyclopentadienyl) dichlorides. A similar correlation was also observ
ed for the fourth ionization potentials of the corresponding Group IVB meta
ls. The correlation between absorption charge-transfer energies and redox g
aps was justified for a series of ansa- and unbridged zirconocene dichlorid
es and dimethyls with variable sandwich ligands. (C) 2000 Elsevier Science
S.A. All rights reserved.