The diphosphaallene radical anion: EPR and theoretical investigations

Abstract

Liquid phase EPR spectra of a diphosphaallenic radical anion have been recorded after electrochemical reduction of a solution of ArP[double bond, length half m-dash]C[double bond, length half m-dash]PAr in THF at 293 K (Ar = 2,4,6-Bu^t₃C₆H₂). The hyperfine coupling interactions of two ³¹P and one ¹³C nuclei (in the case of Ar[double bond, length half m-dash]¹³C[double bond, length half m-dash]PAr) are discussed in the light of AM1 calculations carried out on (ArP[double bond, length half m-dash]C[double bond, length half m-dash]PAr)^˙–, of ab initio calculations performed on the model radical anion (HP[double bond, length half m-dash]C[double bond, length half m-dash]PH)^˙– at the MP2 and MCSCF levels of theory and of DFT calculations on (HP[double bond, length half m-dash]C[double bond, length half m-dash]PH)^˙–. The structure of the radical anion is compared with that of the neutral molecule.

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