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Effects of nitrogen atoms on the stability and reactivity of tricyclic boracarbenes by DFT

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Abstract

Following our quest for novel carbenes, effects of substituting 1 to 5 nitrogen atoms on the stability and reactivity of singlet (s) and triplet (t) forms of 7-boratricyclo[1,1,1,01,7,07,3,07,5]hexa-2-carbylenes (1–20) are compared and contrasted, at B3LYP/aug-cc-pvtz level of theory. All species appear as ground state minima on their energy surface, for showing no negative force constant. Singlets (1s–20s) are ground states and more stable than their corresponding triplets (1t–20t). Reactivity of the species (1s–20s vs. 1t–20t) is discussed in terms of isodesmic reactions, considering nucleophilicity (N), electrophilicity (ω), and heat of hydrogenation. As well as, the addition of nitrogen atoms decreased nucleophilicity (N), while increasing electrophilicity (ω). Despite the enormous steric strain involved in their cubic structures, the most stable scrutinized carbenes appear to be singlet 1,4,5-triaza-7-boratricyclo[1,1,1,01,7,07,3,07,5]hexa-2-carbylene (13) for showing the highest value of ΔEs–t. Such higher stabilization is attributed to a coordinate covalent bond observed between the carbenic center and the boron atom. This study offers new insights into the chemistry of these exotic tricyclic shaped carbenes.

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Acknowledgements

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

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Tarbiat Modares University.

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Authors and Affiliations

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

    Nastaran Abedini & Mohamad Z. Kassaee

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

    Mohamad Z. Kassaee & P. T. Cummings

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  1. Nastaran Abedini
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  2. Mohamad Z. Kassaee
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  3. P. T. Cummings
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Correspondence to Mohamad Z. Kassaee.

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Abedini, N., Kassaee, M.Z. & Cummings, P.T. Effects of nitrogen atoms on the stability and reactivity of tricyclic boracarbenes by DFT. Theor Chem Acc 139, 146 (2020). https://doi.org/10.1007/s00214-020-02659-z

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