Oxidative addition of the C-I bond on aluminum nanoclusters

Turbasu Sengupta, Susanta Das, Sourav Pal

Research output: Contribution to journalArticlepeer-review

17 Scopus citations

Abstract

Energetics and the in-depth reaction mechanism of the oxidative addition step of the cross-coupling reaction are studied in the framework of density functional theory (DFT) on aluminum nanoclusters. Aluminum metal in its bulk state is totally inactive towards carbon-halogen bond dissociation but selected Al nanoclusters (size ranging from 3 to 20 atoms) have shown a significantly lower activation barrier towards the oxidative addition reaction. The calculated energy barriers are lower than the gold clusters and within a comparable range with the conventional and most versatile Pd catalyst. Further investigations reveal that the activation energies and other reaction parameters are highly sensitive to the geometrical shapes and electronic structures of the clusters rather than their size, imposing the fact that comprehensive studies on aluminum clusters can be beneficial for nanoscience and nanotechnology. To understand the possible reaction mechanism in detail, the reaction pathway is investigated with the ab initio Born Oppenheimer Molecular Dynamics (BOMD) simulation and the Natural Bond Orbital (NBO) analysis. In short, our theoretical study highlights the thermodynamic and kinetic details of C-I bond dissociation on aluminum clusters for future endeavors in cluster chemistry.

Original languageEnglish
Pages (from-to)12109-12125
Number of pages17
JournalNanoscale
Volume7
Issue number28
DOIs
StatePublished - 28 Jul 2015
Externally publishedYes

Bibliographical note

Publisher Copyright:
© The Royal Society of Chemistry.

Funding

FundersFunder number
Council of Scientific and Industrial Researchcsc 0129
Department of Science and Technology, Republic of South Africa
University Grants Commission

    Fingerprint

    Dive into the research topics of 'Oxidative addition of the C-I bond on aluminum nanoclusters'. Together they form a unique fingerprint.

    Cite this