A novel molecular tetravalent ethyltriphenylphosphorous dibromide ((C6H5)3PCH2Br2 ) has been synthesized in toluene and has been characterized by single crystal x-ray crystallography. Theoretical studies have been conducted utilizing DFT(B3LYP/6-311+G(d,p) level of theory both in gas phase and solution using diverse solvents. Potential surface energy calculations revealed the existence of the tetravalent diionic form as a global minimum except in dimethylsulfoxide where our adduct is more stable. Calculations showed that the Br-Br bond distance is in quadratic variation with the medium dielectric constant. The unusual Br-Br lengthen is reasonably rationalized in terms of charge transfer of electron density from the clouds in phenyl moieties to the σ* of the dibromine entity. The average harmonic oscillator index of aromaticity of the complex are found suffering a deviation from unity.
Organophosphorous, X-ray, DFT, AHOMA, Hardness