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Synthesis and Properties of Mononuclear Group 10 Alkoxy‐Biscarbene Complexes
Author(s) -
LópezAlberca María P.,
Mancheño María J.,
Fernández Israel,
GómezGallego Mar,
Sierra Miguel A.,
Torres Rosario
Publication year - 2009
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200802147
Subject(s) - alkoxy group , group (periodic table) , chemistry , stereochemistry , organic chemistry , alkyl
New Pd ‐ and Pt‐biscarbenes : The synthesis by the stoichiometric transmetalation reactions from Fischer alkoxy‐chromium(0) carbene complexes of stable mononuclear (palladium and platinum) alkoxy‐biscarbene complexes is reported. The structure, bonding situation, and the electronic and redox properties of these complexes are studied by a combination of experimental and computational (DFT) methods.The synthesis, isolation, and complete characterization (NMR and X‐Ray diffraction techniques) of stable mononuclear (palladium and platinum) alkoxy‐biscarbene complexes is reported. These compounds are easily accessible through stoichiometric transmetalation reactions from Fischer alkoxy‐chromium(0) carbene complexes. By a combination of experimental (UV/Vis spectroscopy, cyclic voltammetry) and computational methods (DFT), the structure, bonding situation, and the electronic and redox properties of these complexes are studied. Although they have structures quite similar, their electronic properties strongly depend on the metal and also on the substitution in the aromatic rings in the aniline moieties. Electron‐withdrawing groups stabilize the HOMO causing the shifting of the oxidation waves to lower anodic potentials in the corresponding cyclic voltammograms.