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Synthesis, Structure, and Reactivity of Carbene-Stabilized Phosphorus(III)-Centered Trications [LP].

Carbene-stabilized [LP] cations have been synthesized for the first time by a reaction between 1-chloro-2,3-bis(dialkylamino)cyclopropenium salts and P(SiMe). In addition, the first structural characterization of such an entity is reported. Consistent with the X-ray data, density functional calculat...

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Publicado en:Journal of the American Chemical Society Vol. 133; no. 51; pp. 20758 - 20761
Autores principales: Petuškova, Jekaterina, Patil, Mahendra, Holle, Sigrid, Lehmann, Christian W., Thiel, Walter, Alcarazo, Manuel
Formato: Artículo
Publicado: American Chemical Society 12/28/2011
Materias:
Carbenes
Organic synthesis
Electron pairs
Density functionals
Ligands (Chemistry)
Acceso en línea:Ver este registro en EBSCOhost
Sumario:Carbene-stabilized [LP] cations have been synthesized for the first time by a reaction between 1-chloro-2,3-bis(dialkylamino)cyclopropenium salts and P(SiMe). In addition, the first structural characterization of such an entity is reported. Consistent with the X-ray data, density functional calculations indicate that these P-centered cations, despite their high positive charge, still feature a nonbonding electron pair on the P-atom (HOMO) and a very low-lying LUMO depicting them as poor σ-donors and excellent π-acceptors.