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Quinobis(imidazolylidene): Synthesis and Study of an Electron‐Configurable Bis(N‐Heterocyclic Carbene) and Its Bimetallic Complexes
Author(s) -
Tennyson Andrew G.,
Ono Robert J.,
Hudnall Todd W.,
Khramov Dimitri M.,
Er Joyce A. V.,
Kamplain Justin W.,
Lynch Vincent M.,
Sessler Jonathan L.,
Bielawski Christopher W.
Publication year - 2010
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.200901883
Subject(s) - chemistry , quinone , cyclic voltammetry , deprotonation , bimetallic strip , metal , redox , carbene , photochemistry , crystallography , infrared spectroscopy , differential pulse voltammetry , osmium , medicinal chemistry , stereochemistry , electrochemistry , inorganic chemistry , organic chemistry , ruthenium , catalysis , electrode , ion
Reaction of bromanil with N , N ′‐dimesitylformamidine followed by deprotonation with NaN(SiMe 3 ) 2 afforded 1,1′,3,3′‐tetramesitylquinobis(imidazolylidene) ( 1 ), a bis(N‐heterocyclic carbene) (NHC) with two NHC moieties connected by a redox active p ‐quinone residue, in 72 % yield of isolated compound. Bimetallic complexes of 1 were prepared by coupling to FcN 3 ( 2 ) or FcNCS ( 3 ; Fc=ferrocenyl) or coordination to [M(cod)Cl] ( 4 a or 4 b , where M=Rh or Ir, respectively; cod=1,5‐cyclooctadiene). Treatment of 4 a and 4 b with excess CO(g) afforded the corresponding [M(CO) 2 Cl] complexes 5 a and 5 b , respectively. Analysis of 2 – 5 by NMR spectroscopy and X‐ray diffraction indicated that the electron‐deficient quinone did not significantly affect the inherent spectral properties or coordination chemistry of the flanking imidazolylidene units, as compared to analogous NHCs. Infrared spectroscopy and cyclic voltammetry revealed that decreasing the electron density at ML n afforded an increase in the stretching energy and a decrease in the reduction potential of the quinone, indicative of metal–quinone electronic interaction. Differential pulse voltammetry and chronoamperometry of the metal‐centered oxidations in 2 – 4 revealed two single, one‐electron peaks. Thus, the metal atoms bound to 1 are oxidized at indistinguishable potentials and do not appear electronically coupled. However, the metal–quinone interaction was used to increase the electron density at coordinated metal atoms. Infrared spectroelectrochemistry revealed that the average ν CO values for 5 a and 5 b decreased by 14 and 15 cm −1 , respectively, upon reduction of the quinone embedded within 1 . These shifts correspond to 10 and 12 cm −1 decreases in the Tolman electronic parameter of this ditopic ligand.