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Dichroic, Dinuclear μ2-(η2-NO)-Nitrosoaniline-Bridged Complexes of Rhenium of the Type [{(CO)3Re(μ-X)}2ONC6H4NR2] (X = Cl, Br, I; R = Me, Et)

✍ Scribed by Christoph Krinninger; Christof Högg; Heinrich Nöth; Juan Carlos Gálvez Ruiz; Peter Mayer; Ondrej Burkacky; Andreas Zumbusch; Ingo-Peter Lorenz


Publisher
John Wiley and Sons
Year
2005
Tongue
English
Weight
245 KB
Volume
11
Category
Article
ISSN
0947-6539

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✦ Synopsis


Abstract

A series of unusual dinuclear μ~2~‐(η^2^‐NO)‐nitrosoaniline‐bridged complexes [{(CO)~3~Re(μ‐X)}~2~ONC~6~H~4~NR~2~] (X = Cl, Br, I; R = Me, Et) with dichroic properties have been synthesised by reaction of pentacarbonylhalogenorhenium(I) [(CO)~5~ReX] (X = Cl, Br, I) with the corresponding nitrosoaniline derivatives R~2~NC~6~H~4~NO (R = Me, Et). The deeply coloured solutions in CH~2~Cl~2~ show broad UV/Vis absorptions from 595 to 620 nm depending on the halogen bridges and N substituents. Single crystals of all six compounds exhibit a pronounced linear dichroism. The molecular structures have been determined by single‐crystal X‐ray analyses. All the compounds contain two face‐shared octahedra, with two halogens and one NO ligand as bridges. The NO ligand coordinates in a nonsymmetrical η^2^‐like fashion with N or O coordination to each Re centre. Therefore, the C‐nitroso group and the planar NC~2~ moiety of NR~2~ both lie almost exactly within the symmetry plane of the dinuclear complexes. These complexes belong to the novel and simple class of neutral dinuclear C‐nitroso complexes that include the rare, non‐assisted μ~2~‐(η^2^‐NO) ligand function and have only single halogen atoms in bridging positions.