Collect. Czech. Chem. Commun. 1993, 58, 1-10

Properties and Reactivity of First and Second Row Hydrides. IV. Interactions Between Hydrides and Their Radical Ions

Rudolf Zahradník

J. Heyrovský Institute of Physical Chemistry and Electrochemistry, Czechoslovak Academy of Sciences, 182 23 Prague 8, Czech Republic


The energies and heats of ion-molecule reactions have been calculated (MP4/6-31G**//6-31G** or better level) and compared with the experimental values obtained from the heats of formation. Two main types of reactions have been studied: (i) AHn + AHn+• ↔ AHn+1+ + AHn-1 (A = C to F and Si to Cl), (ii) AHn + BHm+• ↔ AHn+1+ + BHm-1 or AHn-1+• + BHm+1+ (A and B = C to F). In contrast to (i), processes of type (ii) permit easy differentiation between the proton transfer and hydrogen atom abstraction mechanisms. A third type of interaction involves reactions with radical anions (A = Li to F); comparison was made with analogous processes with radical cations. A brief comment is made about the influence of the level of computational sophistication on the energies and heats of reaction, as well as on the stabilization energy of a hydrogen bonded intermediate, a structure which is similar to that of the reaction products.