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Estimating structure, stability, and electronic properties on halogenated derivatives of 2-germabicyclo[1.1.1.]pentane-2-ylidenes at density functional theory

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Abstract

In this computational survey, substituent effects of group 17 on the stability (singlet–triplet energy gaps, ΔEs–t) and reactivity of singlet (s) and triplet (t) forms of 2-germabicyclo[1.1.1.]pentane-2-ylidenes are considered by using B3LYP/6–311 +  + G**, B3LYP/aug-cc-pvtz, and B3LYP/def2-TZVP level of theories. In all germylene structures, singlets appear more stable than their corresponding triplet congeners, revealing a singlet ground state and the order of stability appears to be 1,3,4,4,5,5-hexachloro-2-germabicyclo[1.1.1.]pentane-2-ylidenes (3) > 1,3,4,4,5,5-hexabromo-2-germabicyclo[1.1.1.]pentane-2-ylidenes (4) > 1,3,4,4,5,5-hexafluoro-2-germabicyclo[1.1.1.]pentane-2-ylidenes (2) > 1,3,4,4,5,5-hexaiodo-2-germabicyclo[1.1.1.]pentane-2-ylidenes (5) > 2-germabicyclo[1.1.1.]pentane-2-ylidenes (1), at the three levels of theory. The positive and negative effects on germylene stability are LP(F, Cl, Br, and I) → LP*G̈e and σ(C-Ge) → σ*(C-F, Cl, Br, and I) interactions, respectively. The results of our calculations show that every singlet germylene with high LP(F, Cl, Br, and I) → LP*G̈e interactions has higher electrophilicity. Also, in going from the most electronegative F to the least electronegative I, the nucleophilicity index (N) for germylene increases. Finally, this survey introduces that germylene 4 s with rather high band gap (ΔEHOMO–LUMO = 97.19 kcal/mol), nucleophilicity (2.20 eV), and stability (ΔEs-t = 76.95 kcal/mol) has high proton affinity (171.55 kcal/mol) that can be applied as multidentate ligands and it is hoped that this will prompt experimental attention toward its.

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Data availability

“Not applicable.”

Code availability

GAMESS program package, (U)B3LYP/6–311 +  + G** level of theory.

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Acknowledgements

The support from Tarbiat Modares University (TMU) is gratefully acknowledged. Special thanks are due to Mrs. Shokufeh Mojtahedi for his continued encouragement and moral support.

Funding

This study is supported by the Tarbiat Modares University.

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Authors and Affiliations

  1. Department of Chemistry, Tarbiat Modares University, Tehran, 14115-175, Iran

    Nastaran Abedini & Mohamad Z. Kassaee

  2. Pure and Applied Research LLC, P.O. Box 111591, Nashville, TN, 37222, USA

    Mohamad Z. Kassaee

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  1. Nastaran Abedini
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  2. Mohamad Z. Kassaee
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Correspondence to Mohamad Z. Kassaee.

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Abedini, N., Kassaee, M.Z. Estimating structure, stability, and electronic properties on halogenated derivatives of 2-germabicyclo[1.1.1.]pentane-2-ylidenes at density functional theory. J Mol Model 28, 207 (2022). https://doi.org/10.1007/s00894-022-05202-y

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  • DOI: https://doi.org/10.1007/s00894-022-05202-y

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