A Review on Molecular Electrochemistry of Metallocene Dichloride and Dimethyl Complexes of Group 4 Metals: Redox Properties and Relation with Optical Ligand-to-Metal Charge Transfer Transitions

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Title:A Review on Molecular Electrochemistry of Metallocene Dichloride and Dimethyl Complexes of Group 4 Metals: Redox Properties and Relation with Optical Ligand-to-Metal Charge Transfer Transitions
Creators:
Loukova, Galina V.
Strelets, Vladimir V.
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 66, 2, pp. 185-206
Uncontrolled Keywords:Titanocenes, EPR spectroscopy, Cyclopentadienyl ligands, Charge transfer, Metallocenes, Zirconocenes, Frontier orbitals, Redox behaviour, Electrochemistry, Electron transition, Substituent effects

Abstract

Emphasis is given to redox, photophysical, and photochemical properties of homologous bent metallocenes of group 4 transition metals. Comparative analysis of a variety of electron-transfer induced transformations and ligand-to-metal charge-transfer excited states is performed for bent metallocene complexes upon systematic variation of the identity of the metal ion (Ti, Zr or Hf), ancillary π- and monodentate σ- (Cl, Me) ligands. For such organometallic π-complexes, linear correlations exist between energies of optical and redox HOMO-to-LUMO electron transitions. It is suggested that combination 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 redox potentials) and the energy gap in metallocene complexes. Some of earlier instructive cases of direct relationship between optical transition energies and differences in redox potentials revealed for inorganic and coordination compounds are discussed. <p>

Title:A Review on Molecular Electrochemistry of Metallocene Dichloride and Dimethyl Complexes of Group 4 Metals: Redox Properties and Relation with Optical Ligand-to-Metal Charge Transfer Transitions
Creators:
Loukova, Galina V.
Strelets, Vladimir V.
Uncontrolled Keywords:Titanocenes, EPR spectroscopy, Cyclopentadienyl ligands, Charge transfer, Metallocenes, Zirconocenes, Frontier orbitals, Redox behaviour, Electrochemistry, Electron transition, Substituent effects
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:66
Number:2
Page Range:pp. 185-206
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc20010185UNSPECIFIED
ID Code:1785
Item Type:Article
Deposited On:06 Feb 2009 17:12
Last Modified:06 Feb 2009 16:12

Citation

Loukova, Galina V.; Strelets, Vladimir V. (2001) A Review on Molecular Electrochemistry of Metallocene Dichloride and Dimethyl Complexes of Group 4 Metals: Redox Properties and Relation with Optical Ligand-to-Metal Charge Transfer Transitions. Collection of Czechoslovak Chemical Communications, 66 (2). pp. 185-206. ISSN 0010-0765

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