Work

Contribution of Nonaxial n → σ* Orbital Interactions in Tetrel Bonding: A Case Study on Si…N Interactions

Year: 2025

Type: article

Abstract: The formation of a σ‐hole interaction is typically associated with a corresponding n → σ* orbital interaction. This study examines the role of these n → σ* interactions in stabilizing Si…N tetrel bonding within various dimeric complexes. While conventional n → σ* orbital overlap along the tetrel bonding axis is observed as expected, the findings highlight the presence and significant contribution of additional nonaxial n → σ* orbital interactions in sp3‐hybridized silicon dimers. Traditional theories of tetrel bonding emphasize linear interactions along the σ‐hole axis, characterized by direct head‐to‐head n → σ* overlaps. However, this study reveals that nonaxially oriented σ* orbitals of the tetrel atom can also substantially interact with electron donors, significantly enhancing the stability of Si…N tetrel bonds. Depending on the substituents in the dimeric complexes, nonaxial n → σ* interactions can contribute notably higher to the stabilization than their axial counterparts.

Source: ChemPhysChem

DOI: 10.1002/cphc.202500042

Authors: Anjali Devi Vasarla, Anik Sen, Rahul Shukla

Institution: GITAM University

Language: English

Topic: Crystallography and molecular interactions

Subfield: Physical and Theoretical Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,550

Funders: Gandhi Institute of Technology and Management, Department of Science and Technology, Ministry of Science and Technology, India, Science and Engineering Research Board