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Functionalization of N 2 to NH 3 via direct N ≡ N bond cleavage using M(III)(NMe 2 ) 3 (M=W/Mo): A theoretical study

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Abstract

Atmospheric N2 can be cleaved directly to yield metal-nitride (before proceeding to the functionalization of N α of coordinated N2) and subsequently functionalized to ammonia using M(III)(NMe2)3 (M = W/Mo) as a catalyst, and suitable proton and electron sources. The calculated energies of thermodynamic and kinetic states of the various intermediates and transition states in the reaction coordinate to yield ammonia confirmed the viability of the proposed reaction pathway. Rationale of different pathways have been examined and discussed in detail. Changes in the structural features of the catalyst and some important intermediates and transition states have also been examined.

N2 can be cleaved directly to form nitride complex and subsequently can be converted to ammonia in the presence of protons and electrons using M(III)(NMe2)3 (M = Mo/W) in a homogeneous solution under normal experimental conditions. The proposed pathway seems to be feasible based on the calculated thermodynamic and kinetic barriers.

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Acknowledgements

Dr. C S thanks the Department of Science and Techno- logy (DST) New Delhi, India for the financial support (No. SR/FT/CS-055/2008). S B gratefully acknowledges the Council of Scientific & Industrial Research (CSIR) for a Senior Research Fellowship (SRF).

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Authors and Affiliations

  1. Catalysis and Energy Laboratory, Department of Chemistry, Pondicherry University, R. V. Nagar, Puducherry, 605 014, India

    SAMBATH BASKARAN, PERUMAL BALU & CHINNAPPAN SIVASANKAR

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  1. SAMBATH BASKARAN
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  2. PERUMAL BALU
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  3. CHINNAPPAN SIVASANKAR
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Correspondence to CHINNAPPAN SIVASANKAR.

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Supplementary Information

Optimized geometries of Mo complexes, energy profiles, tables and Cartesian coordinates for reactants, products, intermediates and transition states are given in Supplementary Information which is available at www.ias.ac.in/chemsci.

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BASKARAN, S., BALU, P. & SIVASANKAR, C. Functionalization of N 2 to NH 3 via direct N ≡ N bond cleavage using M(III)(NMe 2 ) 3 (M=W/Mo): A theoretical study. J Chem Sci 127, 83–94 (2015). https://doi.org/10.1007/s12039-014-0752-3

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