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A planar pentacoordinate sulfur atom.

Palash J Thakuria¹, Kangkan Sarmah¹, Siddharth K Purkayastha¹

¹Advanced Computational Chemistry Centre, Cotton University, Panbazar, Guwahati, Assam, 781001, India. ankurkantiguha@gmail.com.

Chemical Communications (Cambridge, England)

|July 10, 2025

Summary

This summary is machine-generated.

Researchers discovered a stable planar pentacoordinate sulfur atom (ppS) in a [Mg5S6]2- cluster. This finding opens new avenues for experimental detection of this rare atomic configuration.

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Area of Science:

Inorganic Chemistry
Computational Chemistry
Materials Science

Background:

Planar pentacoordinate sulfur atoms (ppS) are exceptionally rare in chemistry.
Only one experimental verification of ppS exists to date.

Purpose of the Study:

To report the discovery of a novel planar pentacoordinate sulfur atom (ppS).
To investigate the stability and structural properties of the [Mg5S6]2- cluster.

Main Methods:

Global structure searches to identify the minimum energy configuration.
Density Functional Theory (DFT) calculations for electronic structure analysis.
Symmetry analysis to confirm the D5h point group.

Main Results:

The global minimum structure of the [Mg5S6]2- cluster features a planar pentacoordinate sulfur atom.
The cluster exhibits perfect D5h symmetry.
Electronic structure calculations indicate significant covalency in the Mg-S bonds.
The dianionic cluster is stable against electron detachment, suggesting experimental feasibility.

Conclusions:

The [Mg5S6]2- cluster represents a stable and experimentally accessible form of planar pentacoordinate sulfur.
The findings challenge existing understanding of sulfur coordination chemistry.
This discovery provides a promising target for future experimental synthesis and characterization.