Early stages of LiX,BeH2X,and BH3X pyrolysis (X stands for NH3 or OH2): A theoretical study of weak dative complex stability

In this work, we study theoretically the thermal decomposition of weak dative complexes (namely, the complexes between BH₃, BeH₂, or LiH and ammonia or water). The most accurate calculations have been carried out at the MP 4sdtq/6-311++G (3df,2p) level on MP 2full/6-31G ** fully optimized geometries. The transition structures for hydrogen evolution are described. The rate constants were obtained using conventional transition-state theory. Stability conditions for the complexes were considered. Water complexes are less stable than are the corresponding ammonia derivatives. Lithium complexes seem to be very unstable. It seems that beryllium compounds could be synthesized. Borane derivatives are known experimentally. We find, as observed, that the first hydrogen evolution occurs only above room temperature. Iminoborane seems not to be easily accessible under pyrolysis conditions. Other reactions require less activation energy. Finally, the early stages of the ammonia–borane pyrolysis and paths to open-chain polymers as well as to cyclic structures are described. © 1993 John Wiley & Sons, Inc.