The distinction between valence electrons and essentially inactive core electrons is the basis of many classifying concepts in chemistry. However, it has recently been recognized that this is an oversimplification and should, at least in some areas of chemistry, be modified. Many cases are known where cations with closed d10 configurations are subject to homoatomic interactions that influence structure and properties. A characteristic and surprisingly uniform structural feature (e.g., of a number of compounds containing monovalent coinage metals) is a clusterlike assembly of d10 cations that corresponds in geometry and bond lengths to fragments of the metal structures themselves. Further evidence for a special type of bonding in such compounds is provided by their physical properties; for example, the absorption in the UV/VIS region shows a drastic redshift and the compounds are often conductors or semiconductors. The d electrons in such cases have obviously lost their pure “core” nature. All bonding models so far proposed for such systems involve mixing of higher orbitals.

Homoatomic d10–d10 Interactions: Their Effects on Structure and Chemical and Physical Properties

Homoatomare d10‐d10‐Wechselwirkungen — Auswirkungen auf Struktur‐ und Stoffeigenschaften

A New Copper Selenide Cluster with PPh3 Ligands: [Cu146Se73(PPh3)30]

Ein neuer Kupferselenidcluster mit PPh3 als Ligand: [Cu146Se73(PPh3)30]

K2Cu5Te5, a Novel Mixed‐Valence Layered Compound with Metallic Properties

Zusammenfassung Bei der Umsetzung von Caesiumcarbonat mit Kupfer und Selen im Temperaturbereich zwischen 850 und 1100 °C konnte neben der bekannten Verbindung Cs3Cu8Se6 ein neues ternares Selenid des Kupfers der Zusammensetzung Cs2Cu5Se4 beobachtet werden. Einkristalluntersuchungen ergaben eine rhombische Elementarzelle mit a = 399,2(3) pm, b = 1941,7(7) pm und c = 1321,9(4) pm (Raumgruppe, Cmcm). Die Struktur ist der des ahnlich zusammengesetzten Cs3Cu8Se3 verwandt: In einer Abfolge von dicht gepackten Schichten aus Selen- und Caesiumatomen sind die Kupferatome in solchen Lucken eingelagert, die ausschliesslich von Selenatomen gebildet werden. Die Abstande der Kupferatome untereinander sind nur wenig grosser als im Metall, und ihre geometrische Anordnung lasst ohne wesentliche Entzerrung einen Ausschnitt aus dem f.c.c. Gitter der Kupferstruktur erkennen, sozusagen ein Fragmentgerust der Atomanordnung des Metalls. Dieses Aufbauprinzip lasst sich auch in den Strukturen anderer metallreicher Chalkogenide des Kupfers und Silbers nachweisen.

Cs2Cu5Se4, ein neues metallreiches kupferselenid mit einer fragmentgerüststruktur des kupfers

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Cs2Cu5Se4, ein neues metallreiches kupferselenid mit einer fragmentgerüststruktur des kupfers