01942nas a2200169   4500008004100000022001400041245006400055210006300119260011000182300001600292490000600308520131200314100002201626700001701648700001601665856009101681       2015                        eng d  a2040-336400aOxidative addition of the C-I bond on aluminum nanoclusters0 aOxidative addition of the CI bond on aluminum nanoclusters  aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcJUN  a12109-121250 v73 a<p>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.</p>1 aSengupta, Turbasu1 aDas, Susanta1 aPal, Sourav  uhttps://library.ncl.res.in/content/oxidative-addition-c-i-bond-aluminum-nanoclusters-0