Exergonic and Spontaneous Production of Radicals through Beryllium Bonds.

High-level ab initio calculations show that the formation of radicals, by the homolytic bond fission of Y-R (Y=F, OH, NH2 ; R=CH3 , NH2 , OH, F, SiH3 , PH2 , SH, Cl, NO) bonds is dramatically favored by the association of the molecule with BeX2 (X=H and Cl) derivatives. This finding is a consequence of two concomitant effects, the significant activation of the Y-R bond after the formation of the beryllium bond, and the huge stabilization of the F(.) (OH(.) , NH2 (.) ) radical upon BeX2 attachment. In those cases where R is an electronegative group, the formation of the radicals is not only exergonic, but spontaneous.