Density Functional Treatment on Alkylation of a Functionalized Deltahedral Zintl Cluster

Abstract

Density functional theory (DFT) is one of the popular methods to understand the electronic structure of molecular systems based on electronic density. On the basis of this theory, several conceptual DFT descriptors have been developed which can deal with the stability, reactivity, and several other physicochemical properties of molecules. Here, we have taken a nine-atom-functionalized deltahedral Zintl cluster of germanium (Ge) to examine the alkylation reaction mechanism. The study showed that the Zintl cluster having a methyl group as a ligand, [Ge9(CH3)3 –], acts as a better nucleophile than the cyanide (−CN)-substituted cluster [Ge9(CN)3 –] in terms of different thermodynamic parameters like free energy, enthalpy of activation, reaction energy, etc. A detailed reaction electronic flux analysis reveals the nature of the electronic activity throughout the reaction pathway. The reaction force, Wiberg bond indices, and dual descriptor lend additional support to the reaction mechanism. It has been found that the alkylation reaction between the Zintl ion and the alkyl halide follows a SN2-like mechanism.

Insights into the Zintl Cluster Mediated Disulfide Bond Separation: A DFT Study

“…In this regard, we thought of a new type of Lewis base i. e., Zintl Lewis base, which can also be used as a nucleophile in S N 2 reaction. [23][24][25] Zintl cluster is polyatomic versatile multianion species belong to a main group compound that exhibits unique reactivity and can participate in diverse chemical transformations. [26][27][28][29][30][31][32] Recently, various studies shown that the nonagermanium based Zintl cluster (Ge 9 ) can be act as a nucleophile due to its presence of external lone pairs.…”

“…Therefore, it is evident that nucleophile agent can be a great reagent for the disulfide bond cleavage. In this regard, we thought of a new type of Lewis base i. e., Zintl Lewis base, which can also be used as a nucleophile in S N 2 reaction [23–25] …”