Direct Access to Palladium(II) Complexes Based on Anionic C,C,C-Phosphonium Ylide Core Pincer Ligand

The reaction of readily available imidazolium-phosphonium salt [MesIm(CH₂)₃PPh₃](OTf)₂ with PdCl₂ in the presence of an excess of Cs₂CO₃ afforded selectively in one step the cationic Pd(II) complex [(C,C,C)Pd(NCMe)](OTf) exhibiting an LX₂-type NHC-ylide-aryl C,C,C-pincer ligand via formal triple C-H bond activation. The replacement of labile MeCN in the latter by CNtBu and CO fragments allowed to estimate the overall electronic properties of this phosphonium ylide core pincer scaffold incorporating three different carbon-based donor ends by IR spectroscopy, cyclic voltammetry, and molecular orbital analysis, revealing its significantly higher electron-rich character compared to the structurally close NHC core pincer system with two phosphonium ylide extremities. The pincer complex [(C,C,C)Pd(CO)](OTf) represents a rare example of Pd(II) carbonyl species stable at room temperature and characterized by X-ray diffraction analysis. The treatment of isostructural cationic complexes [(C,C,C)Pd(NCMe)](OTf) and [(C,C,C)Pd(CO)](OTf) with (allyl)MgBr and nBuLi led to the formation of zwitterionic phosphonium organopalladates [(C,C,C)PdBr] and [(C,C,C)Pd(COnBu)], respectively.