A review on molecular electrochemistry of metallocene dichloride and dimethyl complexes of group 4 metals: Redox properties and relation with opticalligand-to-metal charge transfer transitions
Gv. Loukova et Vv. Strelets, A review on molecular electrochemistry of metallocene dichloride and dimethyl complexes of group 4 metals: Redox properties and relation with opticalligand-to-metal charge transfer transitions, COLL CZECH, 66(2), 2001, pp. 185-206
Citations number
130
Categorie Soggetti
Chemistry
Journal title
COLLECTION OF CZECHOSLOVAK CHEMICAL COMMUNICATIONS
Emphasis is given to redox, photophysical, and photochemical properties of
homologous bent metallocenes of group 4 transition metals. Comparative anal
ysis of a variety of electron-transfer induced transformations and ligand-t
o-metal charge-transfer excited states is performed for bent metallocene co
mplexes upon systematic variation of the identity of the metal ion (Ti, Zr
or Hf), ancillary pi- and monodentate sigma- (Cl, Me) ligands. For such org
anometallic pi -complexes, linear correlations exist between energies of op
tical and redox HOMO-to-LUMO electron transitions. It is suggested that com
bination of spectroscopic and electrochemical techniques provides important
diagnostics to determine "ionisation potential" and "electron affinity" in
solution (relative energies of frontier molecular orbitals obtained as red
ox potentials) and the energy gap in metallocene complexes. Some of earlier
instructive cases of direct relationship between optical transition energi
es and differences in redox potentials revealed for inorganic and coordinat
ion compounds are discussed.