Theoretical design of the biradical character in 1,3-diphosphacyclobutanediyl and homologous structures

Abstract

The electronic nature of 1,3-diphosphacyclobutane-2,4-diyl is explored with wavefunction based and density functional methods. According to MCSCF calculations the singlet state of the title compound is a biradicaloid with closed shell character, the number of unpaired electrons, assigned upon the analysis of the natural orbitals, is close to one. The participation of closed shell contributions in the overall wavefunction arises from a strong mixing of canonical structures, which emphasizes (a) the phosphorane type of bonding as well as (b) π-delocalization within the ring system. The bonding situation changes when σ-attracting substituents, e.g.amino groups, are attached to the phosphorus atoms. They inhibit possible cyclic π-delocalization and enhance the biradical character within the ring system.