| Abstract: | Based on the octadecahedron of eleven-vertex closo-borane,the eleven-vertex closo-heteroborane was suggested with nonmetallic atoms instead of the different nonequivalent boron,and the stabilities were predicted at G96PW91/6-31+G(3d,2p) level.The small heteroatoms,C,N,O,preferentially occupy vertex 2 with the absolutely lowest relative energy to form the high stabilization closo-heteroboranes.They cap four-membered rings to satisfy the geometrical demand of short B-Z bonds.The electron attractions from the vicinal boron atoms make the frameworks shrink.Differently,Si and Ge preferentially substitute for boron at vertex 1 with six tight B-Z bonds and form stabilized molecules.P,As,S,and Se tend to occupy vertex 4 and the optimized structures belong to the nido configurations,in contrast to high electronegative heteroatoms,S and Se transfer less negative charges to framework and the electropositive heteroatoms,Si and Ge transfer more negative charges to framework to form the delocalization structures.The HOMO-LUMO gaps show that most of predicted clusters possess chemical stabilities.The substitutions of heteroatoms for boron atoms in eleven-vertex closo-hcteroboranes are consistent with the topological charge stabilization rule proposed by Gimarc. |
