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

Structure and Bonding in Copper(I) Carbonyl and Cyanide Complexes

Exposing crystalline CuAsF6 to < 1 atm CO produces the homoleptic copper carbonyl cations [Cu(CO)]+, [Cu(CO)2]+, and [Cu(CO)3]+. These complexes were characterized by IR and Raman spectroscopy and by tensimetric titrations. The IR and Raman data are consistent with a two-coordinate, linear structure for the [Cu(CO)2]+ cation and with a three-coordinate, trigonal-planar structure for the [Cu(CO)3]+ ion. The compounds [Cu(CO)2][AsF6] and [Cu(CO)3][AsF6] represent the first examples of isolable polycarbonyls of Cu(I).

[Cu(CO)(n)()](+) Complex Ions in the Solid State (n = 1, 2, 3).

The three-center two-electron (3c-2e) bond is a well-known type of “electron-deficient” interaction that typically involves electron-poor main-group elements, such as aluminum or boron, in combination with strong s-donor ligands, such as hydride or alkyl ligands. However, 3c-2e bonds have also been observed for transition metals, for example in copper(I) aryl complexes in which the electron-deficient bond is supported by an unusually close Cu Cu contact (2.37– 2.45 ) indicative of a cuprophilic interaction. This attractive interaction between copper centers is reminiscent of the M M interactions observed in 3c-2e bonds of main-group metals. Over the past decade, similar cuprophilic interactions have been observed to result from 3c-2e bonds supported by unconventional L-type (two electron) donor interactions involving, for example, phosphole ligands. The latter complexes represent rare examples of a PR3 ligand coordinated in the m-h:h bridging mode. Herein we report the formation of a dicopper complex bridged by acetonitrile in this unusual m-h:h mode, whereby the bridging ligand formally contributes both electrons to the 3c2e interaction. The work discussed herein derives from an interest in dinuclear metal complexes for cooperative substrate activations in catalytic reactions. In particular, the use of dinucleating ligands with rigid frameworks may provide well-defined pockets that promote electronic communication between the metal centers and create selective binding sites for substrates, thereby emulating the role of the protein scaffold in enzymes. For this purpose we developed a ligand system based on 1,8-naphthyridine. The ligand 2,7-bis(1,1-dipyridylethyl)-1,8-naphthyridine (dpen) was synthesized by lithiation of 2,2’-dipyridylethane and subsequent reaction with 2,7dichloro-1,8-naphthyridine [Eq. (1)]. Ligands based on 1,8napthyridine have been shown to support a variety of

Dinucleating Naphthyridine-Based Ligand for Assembly of Bridged Dicopper(I) Centers: Three-Center Two-Electron Bonding Involving an Acetonitrile Donor

Preparation and properties of some carbonyl-bridged dinuclear copper complexes

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Preparation and properties of some carbonyl-bridged dinuclear copper complexes