Copper(I) and Gold(I) Complexes of Aminofunctionalized Phosphinines: Synthesis and Structural Characterization

A series of novel 3-N,N-dimethylaminofunctionalized phosphinines were synthesized and structurally characterized. DFT calculations showed that these aromatic phosphorus heterocycles possess stronger pi -donor and sigma -donor properties compared to the parent phosphinine C5H5P. With CuBr.SMe2, the corresponding complexes of the type [(phosphinine)(2)CuBr](2) are formed, which show the classical terminal sigma -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.SMe2 the phosphinine-based hydrochloride salts forms a rare Cu(I) complex with a Cu4Cl4-core, that contains two pairs of differently coordinating phosphinine ligands.

Automated summary

A series of novel 3-N,N-dimethylaminofunctionalized phosphinines were synthesized and characterized. DFT calculations showed their stronger pi-donor and sigma-donor properties compared to C5H5P. Complexes of [(phosphinine)(2)CuBr](2) and mononuclear phosphinine-Au(I)Cl were obtained and characterized. The presence of SiMe3-group and donor-functionality allows for post-synthetic ligand modifications. A rare Cu(I) complex with a Cu4Cl4-core, containing two pairs of differently coordinating phosphinine ligands, was formed with CuCl.SMe2.