The relative stabilities of 11-vertex nido- and 12-vertex closo-heteroboranes and -borates: facile estimation by structural or connection increments

Abstract

The relative thermodynamic stabilities of ortho-, meta- and para-isomers of 12-vertex closo-heteroboranes and -borates with different p-block heteroatoms were determined using density functional theory. More electronegative (smaller) heteroatoms tend to occupy non-adjacent, whereas less electronegative (larger) heteroatoms tend to occupy adjacent vertices in the thermodynamically most stable closo-diheterododecaborane isomers. The computed relative stabilities agree perfectly with experimental observations. The energy differences of para- and meta- relative to ortho-isomers of 12-vertex closo-heteroboranes generally depend on the extent of electron localization by a given heteroatom and show highly periodic trends, i.e. increase along the period and decrease down the group. The energy penalties for the HetHet structural feature (two heteroatoms adjacent to each other) for the 12-vertex closo-cluster are apparently significantly different from those for the 11-vertex nido-cluster. Reformulating two 11-vertex nido-structural features, i.e. Het_5k(2) and HetHet, in terms of connection increments along with the additional structural feature HetHet_m give the relative stabilities of various isomeric 11-vertex nido- as well as 12-vertex closo-heteroboranes and -borates, using one unique set of increments.