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.
Universidad Autónoma de Madrid, Departamento de Química, Facultad de Ciencias, Módulo 13, Campus de Excelencia UAM-CSIC, Cantoblanco, 28049, Madrid, Spain.
Oriana
O
Brea
Instituto de Química Médica (CSIC)., C/ Juan de la Cierva, 3, 28006, Madrid, Spain.
Ibon
I
Alkorta
Universidad Autónoma de Madrid, Departamento de Química, Facultad de Ciencias, Módulo 13, Campus de Excelencia UAM-CSIC, Cantoblanco, 28049, Madrid, Spain.
Otilia
O
Mó
Universidad Autónoma de Madrid, Departamento de Química, Facultad de Ciencias, Módulo 13, Campus de Excelencia UAM-CSIC, Cantoblanco, 28049, Madrid, Spain. manuel.yanez@uam.es.
Manuel
0000-0003-0854-585X
M
Yáñez
Instituto de Química Médica (CSIC)., C/ Juan de la Cierva, 3, 28006, Madrid, Spain.
José
J
Elguero
Universidad Autónoma de Madrid, Departamento de Química, Facultad de Ciencias, Módulo 13, Campus de Excelencia UAM-CSIC, Cantoblanco, 28049, Madrid, Spain.
Inés
I
Corral
ab initio calculations; beryllium; gas-phase reactions; noncovalent interactions; spontaneous radical formation