ic050747w_si_001.zip (2.26 MB)
Simple Route to the Doubly ortho-Palladated Azobenzenes: Building Blocks for Organometallic Polymers and Metallomesogens
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posted on 2005-08-22, 00:00 authored by Manda Ćurić, Darko Babić, Aleksandar Višnjevac, Krešimir MolčanovA new class of doubly cyclopalladated complexes, {PdCl(dmf)}2(μ-azb) (1) and {PdCl(dmf)}2(μ-aazb) (2), has been prepared in
dimethylformamide (dmf) by reaction of azobenzene (azb) and
4-aminoazobenzene (aazb), respectively, with an excess of
PdCl2(CH3CN)2 complex. Recrystallization of 1 and 2 in dimethyl
sulfoxide (dmso) yields complexes {PdCl(dmso)}2(μ-azb) (3) and
{PdCl(dmso)}2(μ-aazb) (4), respectively. The crystal structures of
1 and 4 have been determined by X-ray diffraction. All complexes
are characterized by 1H and 13C NMR spectra and elemental
analysis. In both crystal structures, solvent molecules are bound
to palladium through oxygen atoms and oriented trans to carbon.
In view of greater preference of palladium to nitrogen and sulfur
atoms, the experimental structures were rationalized by quantum-chemical calculations and confirmed as the most stable isomers.