# From NO to NTe: In Silico Study of Ruthenium Compounds Containing Chalcogenonitrosyl Ligands

## TL;DR

This study uses computational methods to explore the bonding and redox behavior of ruthenium compounds with chalcogenonitrosyl ligands.

## Contribution

The paper introduces a systematic computational analysis of Ru–NE bond behavior under one-electron reduction across a chalcogen series.

## Key findings

- One-electron reduction weakens the Ru–NE bond by a factor of 2.9 to 4.2.
- Reduction causes a ~30° decrease in the Ru–N–E bond angle.
- Spin density and wave function analyses show increased lability of chalcogenonitrosyl ligands after reduction.

## Abstract

Ruthenium compounds bearing chalcogenonitrosyl ligands
(NE, where
E = O, S, Se, Te) represent a unique class of molecules with intriguing
bonding patterns and potential relevance in redox-active systems.
This manuscript presents a systematic investigation of a series of
ruthenium-chalcogenonitrosyl compounds through combined Density Functional
Theory (DFT) and generalized Kohn–Sham energy decomposition
analysis (GKS-EDA) calculations. The compounds were evaluated both
before and after one-electron reduction, focusing on their structural
and electronic properties. Our results reveal clear trends in geometry,
bond strength, and charge distribution, providing insight into the
fundamental bonding interactions that govern the stability and redox
behavior of these species. In particular, we examine the nature of
the Ru–NE bond across the chalcogen series and evaluate the
effects of one-electron reduction on these systems. The results demonstrate
that one-electron reduction favors the labilization of the chalcogenonitrosyl
ligands, as demonstrated by spin density plots and wave function analyses.
The total interaction energy (ΔE
tot) for the Ru–NE bond indicates that, following one-electron
reduction, this interaction is weakened by a factor of 2.9 to 4.2
(from NTe to NO) compared to the neutral species, accompanied by a
decrease in the Ru–N–E angle of approximately 30°.