RESUMO
The synthesis and isolation of a phosphinine selenide was achieved for the first time by reacting red selenium with 2,6-bis(trimethylsilyl)phosphinine. The rather large coupling constant of 1 JP,Se =883â Hz is in line with a P-Se bond of high s-character. The σ-electron donating Me3 Si-substituents significantly increase the energy of the phosphorus lone pair and hence its basicity, making the heterocycle considerably more basic and nucleophilic than the unsubstituted phosphinine C5 H5 P, as confirmed by the calculated gas phase basicities. NBO calculations further reveal that the lone pairs of the selenium atom are stabilized through donor-acceptor interactions with antibonding orbitals of the aromatic ring. The novel phosphinine selenide shows a distinct reactivity towards hexafluoro-2-butyne, Au(I)Cl as well as i PrOH. Our results pave the way for new perspectives in the chemistry of phosphorus in low coordination.
RESUMO
The yet unknown 2-amino-substituted λ3 ,σ2 -phosphinines are phosphorus-containing aniline derivatives. Calculations show that the strong interaction of the π-donating NR2 â group with the aromatic system results in a high π-density at the phosphorus atom. We could now synthesize 2-N(CH3 )2 -functionalized phosphinines, starting from a 3-N(CH3 )2 -substituted 2-pyrone and (CH3 )3 Si-C≡P. Their reaction with CuBrâ S(CH3 )2 affords CuI â complexes with the first example of a neutral phosphinine acting as a rare bridging µ2 -P-4e donor-ligand between two CuI â centers. Our experimental and theoretical investigations show that 2-aminophosphinines are missing links in the series of known 2-donor-functionalized phosphinines.