(Isocyano group)···Lone Pair Interactions Involving Coordinated Isocyanides: Experimental, Theoretical and CSD Study

Inspection of the X-ray structure of the newly prepared trans-[PdCl(CNXyl)ACD] (ADC = XylNH–C=N–[5-iodo-2,6-dimethylpyrimidin-4-yl]) complex made possible the first identification of the π-hole interaction involving the nitrogen atom of coordinated isocyano group toward a lone pair. Processing of availible CSD data and results of DFT calculations revealed the possibility of two different sites for π-hole interaction involving isocyanides, i.e. both isocyano carbon and nitrogen centers are capable of acting as the π-hole donor toward the lone pairs.