Synthesis and electrochemical study of iron, chromium and tungsten aminocarbenes: Role of ligand structure and central metal nature

Several series of Fischer-type aminocarbene complexes with central Fe, Cr or W atoms and with various carbene substitution were synthesized and electrochemically investigated by dc-polarography and cyclic voltammetry. The shifts and changes of reduction and oxidation potentials were evaluated using...

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Bibliographic Details
Published in:Electrochimica acta Vol. 55; no. 27; pp. 8341 - 8351
Main Authors: Hoskovcová, Irena, Roháčová, Jana, Dvořák, Dalimil, Tobrman, Tomáš, Záliš, Stanislav, Zvěřinová, Radka, Ludvík, Jiří
Format: Journal Article Conference Proceeding
Language:English
Published: Kidlington Elsevier Ltd 30.11.2010
Elsevier
Subjects:
Carbenes
Chemistry
Chromium
Electronics
Exact sciences and technology
Fischer aminocarbene complexes
HOMO–LUMO displacement
Iron
LFER
Ligands
Molecular structure
Orbitals
Organic chemistry
Organometalloidal and organometallic compounds
Preparations and properties
Reduction
Structurally dependent redox properties
Transition metals derivatives
Voltammetry–polarography
Voltammetry–polarography
Fischer aminocarbene complexes
LFER
Structurally dependent redox properties
HOMO–LUMO displacement
Chromium Organic compounds
Frontier orbital
Chromium Carbonyl Complexes
Orbital interaction
Organic ligand
Theoretical study
Voltammetry
Transition metal Carbonyl Complexes
Tungsten Organic compounds
Ylidene complex
Iron Organic compounds
Iron Carbonyl Complexes
Electrochemical properties
Polarography
Aminocarbene
Density functional method
Property structure relationship
HOMO-LUMO displacement
Voltammetry-polarography
Chemical synthesis
Tungsten Carbonyl Complexes
ISSN:0013-4686, 1873-3859
Online Access:Get full text
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Summary:Several series of Fischer-type aminocarbene complexes with central Fe, Cr or W atoms and with various carbene substitution were synthesized and electrochemically investigated by dc-polarography and cyclic voltammetry. The shifts and changes of reduction and oxidation potentials were evaluated using the linear free energy relationship (LFER) approach with respect to (a) the type of coordination, (b) the substitution on the carbene ligand and (c) the nature of the central metal atom. The analysis of measured data confirms that the reduction center is localized on the carbene moiety and is strongly influenced by both electronic and sterical properties of its substituents. The oxidation proceeds on the metal and depends mainly on its nature and on the π-acidity of the ligands. Electrochemistry thus represents an important experimental approach to the description and understanding of the molecular electronic structure and redox properties. Experimental results are supported by DFT calculation of HOMO and LUMO orbitals shape and composition.
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ISSN:0013-4686
1873-3859
DOI:10.1016/j.electacta.2010.02.057