Zintl Ions Principles and Recent Developments
R. Bruce King: Structure and Bonding in Zintl Ions and Related Main Group Element ClustersStefanie Gärtner, Nikolaus Korber: Polyanions of Group 14 and Group 15 Elements in Alkali and Alkaline Earth Metal Solid State Compounds and Solvate Structures Bryan
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Structure and Bonding in Zintl Ions and Related Main Group Element Clusters R. B. King
Abstract This chapter reviews the methods that are useful for understanding the structure and bonding in Zintl ions and related bare post-transition element clusters in approximate historical order. After briefly discussing the Zintl-Klemm model the Wade-Mingos rules and related ideas are discussed. The chapter concludes with a discussion of the jellium model and special methods pertaining to bare metal clusters with interstitial atoms. Keywords: Jellium model Metal clusters Wade-Mingos rules Zintl ions Contents 1 2
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Early Efforts to Rationalize the Structures of the Zintl Ions: The Zintl–Klemm Concept . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 3 The Relationship of Zintl Ions to Polyhedral Boranes: The Wade–Mingos Rules and the Aromaticity of Clusters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 3.1 Application of the Wade–Mingos Rules to Polyhedral Boranes: Nido and Arachno Borane Structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 3.2 Aromaticity in Boranes and Related Clusters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 3.3 Application of the Wade–Mingos Rules to Bare Post-Transition Metal Clusters . . . . 10 4 Beyond the Wade–Mingos Rules: The Jellium Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 5 Clusters with Interstitial Atoms: Available Internal Volume Can Override Electronic Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 6 A Cluster Within a Cluster: The Icosahedral Matryoshka Nesting Doll Cluster . . . . . . . . . . . 20 7 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
R.B. King Department of Chemistry, University of Georgia, Athens, GA 30602, USA e-mail: [email protected]
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R.B. King
1 Introduction Anionic species of the post-transition elements date back to the work of Johannis [1, 2] in 1891, who found that reduction of elemental lead with sodium in liquid ammonia gives a green solution apparently containing some type of lead anion. Subsequent detailed studies on this lead anion by Smyth in 1917 [3] suggested a Pb2.25– stoichiometry, or Pb94– with an integral number of lead atoms. As a result of these studies, as well as extensive subsequent work by Zintl and coworkers in the
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