Dihydrogen bonding in main group elements: A case study of complexes of LiH, BH3, and AlH3 with third-row hydrides

A systematic investigation of the occurrence of dihydrogen bonds in the mai n group elements is taken up. The complexes of LiH, BH3, and AlH3 with the third-row hydrides, viz. HCl, H2S, and PH3, as well as their dimers are stu died at the ab initio MP2 level of theory and compared with the correspondi ng second-row hydrides. The dihydrogen bonds in the third-row dimers are we aker than those in the sa end-row ones, with the H ... H distance being gre ater than 2.4 Angstrom in some complexes and dimers. The existence of a bon d between such neighboring hydrogens is established on the basis of topogra phical analysis of electron density. The energy of dihydrogen bonds in the dimers of third-row complexes is similar to the conventional weak H-bonds. The decomposition analysis of interaction energy of dimers shows predominan ce of an electrostatic component followed by polarization and charge transf er. The present study also suggests reinvestigation of the structure of pho sphine-borane (BH3PH3) using the IR and NMR techniques.