Abstract
AbstractA series of novel 3‐N,N‐dimethylaminofunctionalized phosphinines were synthesized and structurally characterized. DFT calculations showed that these aromatic phosphorus heterocycles possess stronger π‐donor and σ‐donor properties compared to the parent phosphinine C5H5P. With CuBr ⋅ SMe2, the corresponding complexes of the type [(phosphinine)2CuBr]2are formed, which show the classical terminal σ‐coordination mode of the phosphorus donor towards the Cu(I) center. Upon reaction with AuCl ⋅ SMe2, mononuclear phosphinine‐Au(I)Cl complexes could be obtained and crystallographically characterized. Moreover, the presence of a SiMe3‐group and a donor‐functionality provide the possibility for post‐synthetic ligand modifications. With CuCl ⋅ SMe2the phosphinine‐based hydrochloride salts forms a rare Cu(I) complex with a Cu4Cl4‐core, that contains two pairs of differently coordinating phosphinine ligands.
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