Department of Chemistry
Indian Institute of Technology Madras, Chennai-600036

Research Proposal Seminar
Exploring the Stability and Bonding of Metal/Non-metal N2/CO Complexes: Through EDA-NOCV calculation
Name: Harsha K Sasidharan, CY20D073
Date & Time: 5/09/2023 & 4.15-5.15 pm
Guide: Dr. Kartik Chandra Mondal, Department of Chemistry Venue: CB310
Abstract:
Nitrogen (N2) is the major component in the earth’s atmosphere (78%), but its inertness hinders most living organisms/animals/plants from using dinitrogen directly to form nitrogen-containing compounds like protein, nucleic acids, nucleotides and amino acids. Microorganisms like rhizobium are known to bind non-polar nitrogen and can convert it into ammonia at ambient conditions. Industrially Haber-Bosch process is known to convert nitrogen to ammonia at high pressure and temperature, but the requirement of extreme conditions reflects the drawback of this process1. Similarly, carbon monoxide is isoelectronic with N2 is a well-known poisonous gas. The activation of CO is difficult as it possesses higher dissociation energy than N2.2 In this context, reaching out to new alternatives to activate N2/CO in milder conditions is necessary. CO is an important ligand in transition metal and organometallic chemistry, transition metal carbonyl complexes gained importance in industrial applications such as Fischer-Tropsch, Cativa and Pauson-Khand reactions. There are several experimentally reported transition metal N2/CO complexes in which nitrogen is activated, cleaved and converted to form metal nitrides and nitrogen-containing compounds, whereas CO is converted to useful products like methanol and acetic acid. Also, non-metal bonded N2/CO complexes are also synthesised and studied. Nowadays, computational calculations like DFT also gained much importance in studying metal/non-metal complexes of nitrogen and carbonyl ligands. EDA-NOCV3-4 calculation is one of the powerful method for understanding and interpreting the bonding scenario in the molecules. The energy decomposition analysis (EDA) developed by Morkuma, Zeigler and Rauk decompose the instantaneous interaction energy between two fragments in a molecule into well-defined chemically meaningful energy terms like electrostatic interaction, Pauli repulsion and orbital interaction energies. The EDA-NOCV approach quantitatively estimates the pairwise contributions of interacting orbitals of the two fragments. There are modelled iron-N2 complexes that are computationally studied and predict their synthesis scope through EDA-NOCV calculations.5 This seminar will give an overview of the computational insights using DFT particularly EDA-NOCV calculations for metal/non-metal N2/CO complexes explaining their bonding interaction in terms of  and  contributions. The stability and strength of the metal/non-metal N2/CO bonds are revealed from the instantaneous interactions obtained from EDA-NOCV calculation thus predicting their synthesis ability in the laboratory.
References:
[1] Masero, F.; Perrin, M.A.; Dey, S.; Mougel, V. Chem. Eur. J. 2021, 27, 3892.
[2] Kalescky, R.; Kraka, E.; Cremer, E. J. Phys. Chem. A. 2013, 117, 8981.
[3] Morokuma, K.; J. Chem. Phys. 1971, 55,1236.
[4] Mitoraj, M.; Michalak, A. Organometallics. 2007, 26, 6576
[5] Gorantla, S. M. N. V. T.; Karnamkkott, H. S; Arumugam, S.; Mondal, S.; Mondal, K. C.; J. Comput. Chem. 2022, 44, 43.


Signature of Guide Signature of HOD