Abstract
Immobilization of palladium(II) acyclic diaminocarbene (Pd(II)-ADC) complexes on a resin support surface has been easily performed by metal-mediated addition of amino groups of benzhydrylamine-polystyrene to the coordinated isocyanide ligand of cis-PdCl2(CNR)2 (R = t-Bu, Cy). The investigation of the benzhydrylamine reaction with palladium-coordinated isocyanides in solution has revealed that, depending on the reaction conditions, two carbene-type complexes can be obtained as a result of the addition to the CN triple bond, as well as a third complex which is formed via substitution of the isocyanide ligand by benzhydrylamine. Nucleophilic addition of an amino group to the isocyanide ligand has led to a cis-acyclic diaminocarbene complex or a cationic diaminocarbene complex with trans configuration and an intramolecular hydrogen-bonded chloride anion (the nature of this noncovalent interaction was analyzed by DFT calculations, including AIM analysis). The unsupported and resin-supported palladium catalysts...
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