Topological Octet-Rule Implementation for Deltahedral Boron Hydrides and Related Zintl Clusters of the Main-Group Elements: Flexible Octet-Rule Fulfillment by Mixed 2- and 3-Center Fractional Bonding Scenarios

Abstract

In the large class of main-group Zintl phases, the octet rule plays a key role for the polyanions following the pseudoatom concept and the 8−N rule, such that a unique correspondence between atomic partial structure and its electron count results. In the conceptual framework of the Wade's type of clusters the relations to the octet rule are less obvious, and its structural implications are not clear. For this purpose, a topological implementation of the octet rule (TORI) within a delocalized bonding scenario is introduced. It is based on the average topology of the deltahedral cluster skeletons and the octet rule applied to delocalized fractional 2-and 3-center bond distributions. For a given skeletal electron pair count SEP, TORI yields values (t toc , y toc ) similar to the styx approach. Two hierarchically different types of octet-rule fulfillment are identified, the cluster-wise and the local one. The local octet-rule fulfillment always implies the cluster-wise one, while the converse is not true. Deltahedral clusters with different skeletal shapes but the same Wade's SEP count can be distinguished with respect to different octet-rule fulfillment. The TORI approach opens a perspective to compare Zintl phases containing Wade-type clusters with those containing 8−N type of partial structures on the basis of octet-rule implications. The main difference to the 8−N type of partial structures identified is the more flexible way of octet-rule fulfillment in the Wade's type clusters, which does not prevent them from realizing the same cluster topology with different SEP counts. The TORI approach works with delocalized fractional bonds and is consistent with the concept of PSEPT; it just adds an additional facet.