Making Aromatic Phosphorus Heterocycles More Basic and Nucleophilic: Synthesis, Characterization and Reactivity of the First Phosphinine Selenide.

ABSTRACT: 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 J_P,Se =883 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 selen

SUBMITTER: Wossidlo F 

PROVIDER: S-EPMC8518535 | biostudies-literature | 2021 Sep

REPOSITORIES: biostudies-literature