A Unique Demonstration of Phosphorous- Silicon Compounds

In 2017 we reported on the first silicon-phosphinidene using a silylene and cAAC:PCl as precursors ( cAAC= cycloalkylaminocarbene). The latter precursor exists in two conformational isomers in solution as well as in the solid... [ view full abstract ]

In 2017 we reported on the first silicon-phosphinidene using a silylene and cAAC:PCl as precursors ( cAAC= cycloalkylaminocarbene). The latter precursor exists in two conformational isomers in solution as well as in the solid state. The existence of the isomers was confirmed by single crystal X-ray structure as well as in solution by ³¹P-NMR.

The reaction of silylene with elemental phosphorus resulted in an acyclic P₄-chain. The in-situ prepared SiCl₂ from HSiCl₃  was used to insert into compounds with P-Cl bonds to yield P-SiCl₃ derivatives. The latter were reduced to low coordinate and low valent P-Si compounds, which were stabilized by NHC and cAAC ligands and showed distinct differences in their physical properties. A radical intermediate was characterized by EPR spectroscopy as the (cAAC)₂Si₂(P-Tip)₂°^- anion. 

The reactions of silylene with RCP compounds will be reported.