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New N-heterocyclic plumbylenes (NHPbs) and their complexes with palladium and platinum by DFT

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Abstract

Following our quest for stable group 14 divalents, novel N-heterocyclic plumbylenes (NHPbs), composed of 2,4,6-cycloheptatriene-2,7-diazaplumbylene (1), benzannulated with one (2), two (3, 4), and three benzene rings (5), are compared and contrasted at the density functional theory level. Results indicate that in going from 1 to 5, the absolute values of singlet-triplet energy gap (ΔEs-t) and band gap (ΔEH-L) increase, while nucleophilicity (N), electrophilicity (ω), and chemical potential (μ) decrease. The most benzannulated structure, ([a,c,e]tribenzo)cyclohepta-2,7-diazaplumbylene (5), turns out as the most stable plumbylene for showing the most negative ΔEs-t of − 194.94 kcal/mol. Furthermore, 5 shows the highest ΔEH-L (− 2.75 eV), with the lowest N (1.31 eV), ω (8.20 eV), μ (− 7.15 eV), and charge of (+ 0.736) on Pb atom. Isodesmic reactions of 1-5 with common transition metal halides, MX2, give forty new metal complexes of 1M-X-5M-X, where M = Pt and Pd, while X = F, Cl, Br, and I. Their complexation energies (ΔECom) indicate that 1-5 are rather stronger ligands with Pt than Pd. Bader’s atoms in molecules (AIM) and NBO analyses show the partial covalent and partial electrostatic nature of Pb-M bonds.

We have scrutinized novel N-heterocyclic plumbylenes (NHPbs: 1-5), by DFT. Structure 5 turns out as the most stable plumbylene for showing the highest ΔEs-t. It shows the highest ΔEH-L with the lowest N, ω, μ, and charge on Pb atom. The results show that NHPbs form stronger complexes with Pt atom than Pd.

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Acknowledgments

Special thanks are due to Seyed Abdolreza Miran, Maniya Sadat Miran, and Seyed Manny Miran for their continued encouragement and moral support.

Funding

We gratefully acknowledge Tarbiat Modares University for financial support.

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Authors and Affiliations

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

    Nazanin Mohebi & Mohamad Zaman Kassaee

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  1. Nazanin Mohebi
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  2. Mohamad Zaman Kassaee
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Correspondence to Mohamad Zaman Kassaee.

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Mohebi, N., Kassaee, M.Z. New N-heterocyclic plumbylenes (NHPbs) and their complexes with palladium and platinum by DFT. Struct Chem 32, 731–757 (2021). https://doi.org/10.1007/s11224-020-01603-y

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