(Isocyano group)lone pair interactions involving coordinated isocyanides: experimental, theoretical and CSD studies

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