Issue 21, 2004

Endohedral nickel and palladium atoms in metal clusters: analogy to endohedral noble gas atoms in fullerenes in polyhedra with five-fold symmetry

Abstract

Nickel and palladium atoms with their closed-shell d10 electronic configurations are encapsulated in the icosahedral clusters [Ni@Ni10E2(CO)18]4− (E = Sb, Bi, Sb→Ni(CO)3, CH3Sn and n-C4H9Sn) and the geometrically related pentagonal antiprismatic cluster Pd@Bi104+ found in Bi14PdBr16. Such endohedral d10 atoms in pentagonal antiprismatic clusters are donors of zero skeletal electrons and interact only weakly with the atoms in the surrounding polyhedron so that they may be regarded as analogous to endohedral noble gases in fullerenes such as He@C60. On the other hand, endohedral nickel and palladium atoms in 10- and 11-vertex flattened deltahedral bare metal clusters of group 13 metals without five-fold symmetry, such as Ni@E1010− found in Na10NiE10 (E = Ga, In) and Pd@Tl117− found in A8Tl11Pd (A = Cs, Rb, K), interact significantly with the cluster atoms, particularly those at the flattened vertices of the deltahedron. The role of endohedral d10 atoms Ni and Pd in polyhedra with five-fold symmetry as “pseudo-noble-gases” can be related to their positions at the “composite divide” of the “Metallurgists' Periodic Table” proposed by H. E. N. Stone on the basis of alloy systematics as well as the equivalence of the five d orbitals in polyhedra with five-fold symmetry.

Graphical abstract: Endohedral nickel and palladium atoms in metal clusters: analogy to endohedral noble gas atoms in fullerenes in polyhedra with five-fold symmetry

Article information

Article type
Perspective
Submitted
13 May 2004
Accepted
16 Aug 2004
First published
31 Aug 2004

Dalton Trans., 2004, 3420-3424

Endohedral nickel and palladium atoms in metal clusters: analogy to endohedral noble gas atoms in fullerenes in polyhedra with five-fold symmetry

R. B. King, Dalton Trans., 2004, 3420 DOI: 10.1039/B407249A

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