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A Quest for (sila)0-4cyclopentasilylenes and their Arduengo Analogs by DFT

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Abstract

Following our interest in exotic silylenes, here we compare and contrast 20 novel five-membered cyclic silylenes, including saturated (sila)0–4 cyclopentasilylenes (1–10) and unsaturated (sila)0-4cyclopentasilylenes-3-ene (1′-10′), reached at B3LYP/6–311++G** level of theory. Arduengo-type silasilylenes 1′-10′ turn out more stable than their corresponding 1–10, for showing higher singlet-triplet energy gap (ΔEs-t), with positive Gibbs free energy of hydrogenation (ΔGover). The band gaps (ΔEH-L) decrease by increasing the number of silicon atoms. Except for non-planar 10′, 6′, and 9′, every 1–10 turns out more nucleophilic than its corresponding 1′-10′. The highest nucleophilicity (N), proton affinity (PA), chemical potential (μ), dihedral angle (D̂), reactivity, and the lowest NBO charge on the divalent Si atom is exhibited by Si-saturated 10′.

Increasing silicons in 1–10 (and 1′-10′) decreases singlet-triplet energy gap (ΔEs-t). Every unsaturated 1′-10′ turns out more stable than its corresponding saturated 1–10 analog. As the most non-planar silylene, 10′ exhibits the highest nucleophilicity (N), proton affinity (PA), chemical potential (μ), dihedral angle \( \left(\hat{\mathrm{D}}\right), \) reactivity, and the lowest NBO charge on divalent Si atom.

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Acknowledgements

We gratefully appreciate Tarbiat Modares University for financial support.

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  1. Department of Chemistry, Tarbiat Modares University, Tehran, Iran

    Mojgan Ayoubi-Chianeh & Mohamad Z. Kassaee

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  1. Mojgan Ayoubi-Chianeh
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Correspondence to Mohamad Z. Kassaee.

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Ayoubi-Chianeh, M., Kassaee, M.Z. A Quest for (sila)0-4cyclopentasilylenes and their Arduengo Analogs by DFT. Silicon 13, 939–960 (2021). https://doi.org/10.1007/s12633-020-00441-1

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