Planar Hexacoordinate Silicon

TL;DR

This paper reports the discovery of stable planar hexacoordinate silicon in specific cluster molecules, revealing unique bonding motifs involving multiple Si-E bonds and electrostatic interactions.

Contribution

It introduces a new class of stable planar hexacoordinate silicon structures with novel bonding patterns in SiE3M3+ clusters.

Findings

Stable planar hexacoordinate silicon observed in SiE3M3+ clusters.

Three Si-E multiple bonds are crucial for planarity and stability.

Electrostatic interactions vary with E electronegativity, enabling unique bonding.

Abstract

The occurrence of planar hexacoordination is very rare in cluster chemistry, particularly for main group elements. We report here a class of planar hexacoordinate silicon (phSi) in the global minimum isomer of SiE3M3+ (E = N, P, As, Sb; M = Ca, Sr, Ba). Three Si-E multiple bonds between phSi and E centers is a key structural and electronic prerequisite for the observation of their prefect planarity and high stability. Especially, the electrostatic interactions between phSi and three M centers become less repulsive with decrease in electronegativity of E. Eventually, a sizable electrostatic attractive interaction exists in between phSi and M centers in SiSb3M3+, leading to a true unprecedented phSi bonding motif which features three Si-Sb multiple bonds and three Si-M ionic bonds.