De-aromatizing Phosphole

Eric Mattmann (1) , François Mathey (1) , Alain Sevin (2) , Gilles Frison (2)

1 DCPH - Laboratoire Hétéroéléments et Coordination
2 LCT - Laboratoire de chimie théorique

Quantum-chemical DFT calculations using the B3LYP functionals have been carried out for 1-Rsubstitued phospholes and some 1-R-substitued 3,4-dimethylphospholes where R ) H, Me, Ph, CN, OH, OMe, F, Cl, and Br. The aromaticity of the phospholyl rings is interpreted as a function of geometric, magnetic, and energetic indexes. It is shown, in agreement with previous experimental results, that phosphole aromaticity does not correlate with pyramidality at phosphorus. Variation of hyperconjugative and, to a lesser extent, conjugative effects is responsible for the change in cyclic delocalization for the phospholes studied here.

Mots clés: REDUCED PYRAMIDAL CHARACTER; TRICOORDINATE PHOSPHORUS; QUANTITATIVE CONCEPT; ELECTRONIC-STRUCTURE; AROMATICITY; ORBITALS; PLANAR; PHOSPHOLE; HETEROCYCLES

Domaines: Chimie théorique et/ou physique; Chimie organique

Eric Mattmann, François Mathey, Alain Sevin, Gilles Frison. De-aromatizing Phosphole. Journal of Organic Chemistry, 2002, 67, pp.1208-1213. ⟨10.1021/jo0108156⟩. ⟨hal-00463046⟩