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Structures and electronic properties of cobalt(II) selone coordination complexes.

Shaydel M Purcell¹, Eric W Reinheimer², Jamie S Ritch¹

¹Department of Chemistry, The University of Winnipeg, 515 Portage Ave, Winnipeg, MB R3B 2E9, Canada.

Acta Crystallographica. Section C, Structural Chemistry

|November 26, 2025

Summary

This study presents new cobalt(II) coordination complexes with selenourea ligands, revealing insights into their structural chemistry and cobalt-selenium bond strengths. The findings contribute to understanding coordination modes in metal complexes.

Keywords:

cobalt(II) complex coordination chemistry crystal structure density functional theory selenourea ligand thermochemistry

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Area of Science:

Inorganic Chemistry
Coordination Chemistry
Structural Chemistry

Background:

Selenourea ligands exhibit diverse structural chemistry.
Coordination complexes involving cobalt and selenourea ligands are infrequently reported.
Imidazole-2-selones are a class of selenourea ligands with potential in coordination chemistry.

Purpose of the Study:

To synthesize and characterize novel cobalt(II) coordination complexes with 1,3-dialkyl-substituted imidazole-2-selone ligands.
To investigate the solid-state structures of these new cobalt complexes.
To compare the observed coordination modes with existing literature and explore factors influencing cobalt-selenium bond strengths.

Main Methods:

Synthesis of cobalt(II) complexes using two different crystallization techniques.
Single-crystal X-ray diffraction analysis to determine the solid-state structures of the complexes.
Density functional theory (DFT) calculations to evaluate cobalt-selenium bond strengths.

Main Results:

The solid-state structures of dichloridobis(1,3-diethylimidazole-2-selone-κSe)cobalt(II) and dichloridobis(1,3-diisopropylimidazole-2-selone-κSe)cobalt(II) were determined.
Complexes predominantly exhibit terminal binding modes of the selenourea ligands, contrasting with bridging modes common in late d-block metals.
DFT calculations indicated a trend in cobalt-selenium bond strengths: Me ≃ Et < iPr for 1,3-dialkyl-substituted imidazole-2-selones.

Conclusions:

The study successfully synthesized and structurally characterized new cobalt(II)-selenourea complexes.
The findings highlight the preference for terminal coordination modes in these specific cobalt complexes.
A clear trend in cobalt-selenium bond strength related to alkyl substitution was computationally established, offering valuable structure-property relationships.