Chapter 4
Halogenation of Metal Clusters
It has been proposed a unified view of principles could be avaliable to determine the
stability of ligand-protected metal clusters via wet chemistry and halogen-passivated
metal cluster in gas phase [1–3]. Typicl examples not only include Au 102 (SR) 44 ,
Au 39 (PR 3 ) 14 X 6 , Au 11 (PR 3 ) 7 X 3 and Au 13 (PR 3 ) 10 X 2 where X is either a halogen or
a thiolate [1], but also shed light on the notable Al 13 I 2n and Al 14 I y series where the
presence of iodine at balanced sites give rise to enhanced stability of the aluminum
iodide clusters [3–5]. These clusters generally have a filled spherical electronic
shell, a compact/symmetric core, balanced charge distribution, and complete steric
protection, along with a relatively large HOMO–LUMO energy gap, pertaining to
superatomic metal cluster characteristic [2].
Similar to halogenation of organic compounds, the halogenation in cluster reactions also embodies several pathways rendering the addition of one or more halogen
atoms to a cluster. The stoichiometry of halogenation in cluster reactivity depends
on both electronic and geometric structural features of the cluster, as well as of
the specific halogen-donor reactant. Halogenation reactions are important in chemical synthesis processes, and halide products are useful intermediates serving as
branching points in the synthesis of numerous functionalized materials [6–13].
In this chapter, we illustrate how metal clusters and even metal cluster complexes
undergo halogenation with inorganic halogen reactants. It is worth noting that, a novel
13-atoms aluminum cluster has been recognized as superhalogen. In this regard,
halogenation of such superatom clusters will fuel more research interest in this area.
It has been recognized that the utilization of superstorms in materials synthesis
contributes to a new generation of nanostructured materials [14–30].
© The Editor(s) (if applicable) and The Author(s), under exclusive license
to Springer Nature Singapore Pte Ltd. 2020
Z. Luo and S. N. Khanna, Metal Clusters and Their Reactivity,
https://doi.org/10.1007/978-981-15-9704-6_4
57
Halogenation of Metal Clusters
It has been proposed a unified view of principles could be avaliable to determine the
stability of ligand-protected metal clusters via wet chemistry and halogen-passivated
metal cluster in gas phase [1–3]. Typicl examples not only include Au 102 (SR) 44 ,
Au 39 (PR 3 ) 14 X 6 , Au 11 (PR 3 ) 7 X 3 and Au 13 (PR 3 ) 10 X 2 where X is either a halogen or
a thiolate [1], but also shed light on the notable Al 13 I 2n and Al 14 I y series where the
presence of iodine at balanced sites give rise to enhanced stability of the aluminum
iodide clusters [3–5]. These clusters generally have a filled spherical electronic
shell, a compact/symmetric core, balanced charge distribution, and complete steric
protection, along with a relatively large HOMO–LUMO energy gap, pertaining to
superatomic metal cluster characteristic [2].
Similar to halogenation of organic compounds, the halogenation in cluster reactions also embodies several pathways rendering the addition of one or more halogen
atoms to a cluster. The stoichiometry of halogenation in cluster reactivity depends
on both electronic and geometric structural features of the cluster, as well as of
the specific halogen-donor reactant. Halogenation reactions are important in chemical synthesis processes, and halide products are useful intermediates serving as
branching points in the synthesis of numerous functionalized materials [6–13].
In this chapter, we illustrate how metal clusters and even metal cluster complexes
undergo halogenation with inorganic halogen reactants. It is worth noting that, a novel
13-atoms aluminum cluster has been recognized as superhalogen. In this regard,
halogenation of such superatom clusters will fuel more research interest in this area.
It has been recognized that the utilization of superstorms in materials synthesis
contributes to a new generation of nanostructured materials [14–30].
© The Editor(s) (if applicable) and The Author(s), under exclusive license
to Springer Nature Singapore Pte Ltd. 2020
Z. Luo and S. N. Khanna, Metal Clusters and Their Reactivity,
https://doi.org/10.1007/978-981-15-9704-6_4
57