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C → N coordination bonds in (CCC) → N+ ← (L) complexes

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Abstract

Quantum chemical calculations were performed on a series of novel divalent NI compounds, CCC → N+ ← CO (1), CCC → N+ ← N2 (2), CCC → N+ ← PPh3 (3), CCC → N+ ← C(NH2)2 (4), CCC → N+ ← NHCMe (5) CCC → N+ ← N-methyl-4-pyridylidene (6) and CCC → N+ ← Cyclopropenylidene (7), where CCC is a carbocyclic carbene (cyclohexa-2,5-diene-4-(diaminomethynyl)-1-ylidene). Complete optimization of 3D structures indicates that the chosen structures are the global minima on their respective potential energy surfaces (tautomeric alternatives are much less stable). The CCC → N+ coordination bond length is in the range of 1.353–1.399 Å, supporting the C → N coordination bond character. This is also supplemented by very low CCC → N bond rotational barriers (> 8 kcal/mol). The CCC → N ← L angles are in the range of 118°–131°, suggesting that there is no heteroallene-type character at the central nitrogen atom. Electron localization function, lone pair occupancy calculations and partial charge analysis indicate the presence of excess electron density at the N+ centre. The nucleophilicity of the designed compounds was further measured by calculating the proton affinity and complexation energies with various Lewis acids like BH3, AlCl3 and AuCl at the N+ centre. All these studies suggest the presence of divalent NI character in the designed compounds 1–7.

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Acknowledgements

The authors thank Council of Scientific and Industrial Research, New Delhi, India, for Senior Research Fellowship and Department of Science and Technology (DST) Government of India, New Delhi, India, for the financial support.

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Authors and Affiliations

  1. Department of Medicinal Chemistry, National Institute of Pharmaceutical Education and Research, Sector 67, S.A.S. Nagar, Punjab, 160062, India

    Neha Patel, Balu Falke & Prasad V. Bharatam

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  1. Neha Patel
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  2. Balu Falke
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  3. Prasad V. Bharatam
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Correspondence to Prasad V. Bharatam.

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Published as part of the special collection of articles “First European Symposium on Chemical Bonding”.

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Patel, N., Falke, B. & Bharatam, P.V. C → N coordination bonds in (CCC) → N+ ← (L) complexes. Theor Chem Acc 137, 34 (2018). https://doi.org/10.1007/s00214-018-2208-1

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