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Borasilylenes in Focus: Topological Effects of Nitrogen Atoms by DFT

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Abstract

DFT calculations in combination with appropriate isodesmic reactions are employed to assess topological effects of nitrogens on thermodynamic parameters of novel mono-, di-, tri-, tetra-, and pentaaza-7-boratricyclo[1,1,1,01,7,07,3,07,5]hexa-2-silylenes (1–20). Despite the enormous steric strain involved in their cubic structures, all our scrutinized singlet and triplet silylenes (1s-20s vs. 1t-20t, respectively) appear as minima on their energy surfaces, for showing singlet ground states. The highest stability (ΔEs−t) is achieved by 1,3,5-triaza-7-boratricyclo[1,1,1,01,7,07,3,07,5]hexa-2-silylene (11), where all the three nitrogens are bonded to the central boron atom. All of our silylenes show the same trend for their calculated ΔΕs−t and band gap (ΔΕHOMO−LUMO). Isodesmic reactions are employed to compare and contrast nucleophilicity (N), electrophilicity (ω), and heat of hydrogenation (ΔEH) for our 40 silylenes (1s-20s vs. 1t-20t). In fact, we introduce a novel generation of tridimensional silylenes which have the intrinsic potential of expanding the existing boundaries of semiconductors, cumulated multi-dentate ligands, etc..

There are 40 novel borasilylenes with an unprecedented common framework that can accommodate up to five nitrogen heteroatoms. They include singlet (s) and triplet (t) mono-, di, tri-, tetra-, and pentaaza-7-boratricyclo[1,1,1,01,7,07,3,07,5]hexa-2-silylenes. They are compared and contrasted with respect to their geometrical parameters, thermodynamic stabilities, isodesmic reactions, at B3LYP/AUG-cc-pVTZ//B3LYP/6-311 + + G** level of theory. Despite the enormous steric strain involved in their cubic structures, all our scrutinized singlet and triplet silylenes appear as minima on their energy surfaces

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Acknowledgements

The support from Tarbiat Modares University (TMU) is gratefully acknowledged.

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Authors and Affiliations

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

    Nastaran Abedini & Mohammad Zaman Kassaee

  2. Chemical and Biomolecular Engineering, Vanderbilt University, Nashville, TN, 37240, USA

    Mohammad Zaman Kassaee & Peter T. Cummings

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  1. Nastaran Abedini
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  2. Mohammad Zaman Kassaee
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  3. Peter T. Cummings
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Correspondence to Mohammad Zaman Kassaee.

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Mohammad Zaman Kassaee is a visiting scholar (sabbatical).

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Abedini, N., Kassaee, M.Z. & Cummings, P.T. Borasilylenes in Focus: Topological Effects of Nitrogen Atoms by DFT. Silicon 13, 3377–3383 (2021). https://doi.org/10.1007/s12633-020-00745-2

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