Authors: Marija H. Habicht, Friedrich Wossidlo, Tobias Bens, Pidko E.A., Christian Müller
The [4+2] cycloaddition reaction between 2‐pyrone and Me3Si−C≡P gives the corresponding 2‐(trimethylsilyl)‐λ3‐phosphinine in good yields as a rather air and moisture stable, colorless oil. Insight into the regioselectivity of the pericyclic reaction was obtained with the help of deuterium‐labeling experiments. The silyl‐phosphinine acts as a ligand for the preparation of a Cu(I) and the first crystallographically characterized phosphinine‐Ag(I) complex. The title compound was further used as a starting material for an alternative preparation of the parent phosphinine C5H5P by means of protodesilylation with HCl. C5H5P reacts with CuBr⋅S(CH3)2 to give an infinite Cu(I)Br coordination polymer. DFT calculations shed light on the influence of the ‐Si(CH3)3 group on the electronic properties of the aromatic phosphorus heterocycle.
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