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Erschienen in:
The Chemical Bond: Lewis and Kossel’s Landmark Contribution Kapitel lesen Erstes Kapitel lesen

2016 | OriginalPaper | Buchkapitel

Structure and Bonding Patterns in Large Molecular Ligated Metal Clusters

verfasst von : Jean-Yves Saillard, Jean-François Halet

Erschienen in: The Chemical Bond I

Verlag: Springer International Publishing

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Abstract

Although there will always be an Edisonian component to a search for new cluster compounds, the greater the understanding of the underlying chemistry, the more focused and efficient the search. It is why the rapid expansion of the synthesis and characterization of ligated transition-metal clusters over the last decades has been accompanied by theories about their bonding and electronic properties with the aid of conceptual ideas and theoretical models such as the development of electron-counting rules which govern the relationship between the structure and the electron count. This review summarizes these theoretical models, their historical development, their limits, and using a selection of specific examples among the extensive panoply of large ligated metal clusters available in the literature, shows how they can help in understanding their structural and electronic properties.

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Vorheriges Kapitel Gilbert Lewis and the Model of Dative Bonding
Nächstes Kapitel Electronic Properties of Endohedral Clusters of Group 14
Fußnoten
1
In some cases, nonbonding orbitals can be unoccupied because lying too high in energy for being accessible.
 
2
This process is nicely detailed for the octahedron example in Ref. [7].
 
3
Organometallic chemists often count electrons in adding to the skeletal electrons all the other electrons lying in the metal coordination sphere, but not participating significantly to the skeletal bonding. An ML3 fragment will thus contribute to this count with 12 additional electrons (6 nonbonding “t 2g ” d-type electrons and the 6 electrons coming from the ligands) (see Fig. 1). Within this electron-counting scheme, [Ru6(CO)18]2−, and [Ru4(CO)12Bi2] are 86 (14 + 6 x 12) and 62 (14 + 4 x 12) electron species, respectively.
 
4
This simple rule may not apply in the case of multicapped clusters, but symmetry considerations may be used to evaluate the number of additional bonding MOs present (see Ref [7]).
 
5
Variations of this model can be found in Refs. [89, 90].
 
6
The tetracapped tetrahedron can also accommodate 8 electrons (see ref. [117]).
 
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Metadaten
Titel
Structure and Bonding Patterns in Large Molecular Ligated Metal Clusters
verfasst von
Jean-Yves Saillard
Jean-François Halet
Copyright-Jahr
2016
Buch
The Chemical Bond I

Print ISBN: 978-3-319-33541-4

Electronic ISBN: 978-3-319-33543-8

Copyright-Jahr: 2016

DOI
https://doi.org/10.1007/430_2015_210

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