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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Vydáno v:	Electrochimica acta Ročník 55; číslo 27; s. 8341 - 8351
Hlavní autoři:	Hoskovcová, Irena, Roháčová, Jana, Dvořák, Dalimil, Tobrman, Tomáš, Záliš, Stanislav, Zvěřinová, Radka, Ludvík, Jiří
Médium:	Journal Article Konferenční příspěvek
Jazyk:	angličtina
Vydáno:	Kidlington Elsevier Ltd 30.11.2010 Elsevier
Témata:	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
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Shrnutí:	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.
Bibliografie:	ObjectType-Article-2 SourceType-Scholarly Journals-1 ObjectType-Feature-1 content type line 23
ISSN:	0013-4686 1873-3859
DOI:	10.1016/j.electacta.2010.02.057