Molecular insights of metal-metal interactions in transition metal complexes using computational methods

Computational methods were used to analyse the interactions around the metal centres in three transition metal (TM) complexes for which the X-ray data are available. We were particularly interested in understanding the metal–metal interactions. We used concepts of bond order, natural population, quantum theory of atom in molecules, electron localisation functions (ELFs) and non-covalent interactions (NCIs). Our results indicate that these tools can be used effectively to help in having insights into the bonding of TM complexes.The Higher Education Commission (HEC) of Mauritius and the South African National Research Foundation.https://www.degruyter.com/journal/key/pac/htmlam2022Chemistr

Theoretical Study of a Derivative of Chlorophosphine with Aliphatic and Aromatic Grignard Reagents: SN2@P or the Novel SN2@Cl Followed by SN2@C?

The proposed SN2 reactions of a hindered organophosphorus reactant with aliphatic and aromatic nucleophiles [Ye et al., Org. Lett. 19, 5384–5387 (2017)] were studied theoretically in order to explain the observed stereochemistry of the products. Our computations indicate that the reaction with the aliphatic nucleophile occurs through a backside SN2@P pathway while the reaction with the aromatic nucleophile proceeds through a novel SN2@Cl mechanism, followed by a frontside SN2@C mechanism. To the best of our knowledge, this is the first time that a SN2@Cl mechanism is reported. We also found that on reducing the bulkiness of substituents around the phosphorus atom, the backside SN2@P mechanism is preferred. The conclusions made from investigating the steric effect should help experimentalists to decide for the organophosphorus reactant to achieve the products of desired stereochemistry.</p

Activation Strain Analyses of Counterion and Solvent Effects on the Ion-Pair S(N)2 Reaction of NH2-and CH3Cl

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