کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
190459 459699 2010 11 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Synthesis and electrochemical study of iron, chromium and tungsten aminocarbenes: Role of ligand structure and central metal nature
کلمات کلیدی
موضوعات مرتبط
مهندسی و علوم پایه مهندسی شیمی مهندسی شیمی (عمومی)
پیش نمایش صفحه اول مقاله
Synthesis and electrochemical study of iron, chromium and tungsten aminocarbenes: Role of ligand structure and central metal nature
چکیده انگلیسی

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.

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Electrochimica Acta - Volume 55, Issue 27, 30 November 2010, Pages 8341–8351
نویسندگان
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