The yet unknown 2-amino-substituted λ ,σ -phosphinines are phosphorus-containing aniline derivatives. Calculations show that the strong interaction of the π-donating NR group with the aromatic system results in a high π-density at the phosphorus atom. We could now synthesize 2-N(CH ) -functionalized phosphinines, starting from a 3-N(CH ) -substituted 2-pyrone and (CH ) Si-C≡P. Their reaction with CuBr⋅S(CH ) affords Cu complexes with the first example of a neutral phosphinine acting as a rare bridging μ -P-4e donor-ligand between two Cu centers. Our experimental and theoretical investigations show that 2-aminophosphinines are missing links in the series of known 2-donor-functionalized phosphinines.
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