Geometrical and Electronic Structures of Dinuclear Complex Ions {(μ-bpym)[Cu(EAr3)2]2}2+ with Intramolecular “Organic Sandwich” Formation (E = P or As; Ar = Aryl; bpym = 2,2‘-Bipyrimidine)

• Published in: Inorganic chemistry 2005-06, Vol.44 (13), p.4637-4643
• Main Authors: Sieger, Monika, Vogler, Conny, Klein, Axel, Knödler, Axel, Wanner, Matthias, Fiedler, Jan, Záliš, Stanislav, Snoeck, Theo L, Kaim, Wolfgang
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic050207z

The compound {(μ-bpym)[Cu(AsPh3)2]2}(BF4)2 (1) has been prepared and studied in comparison with the triphenylphosphine analogue 2. Qualitatively, the structure of 1 with characteristically distorted copper(I) coordination caused by Ph/bpym/Ph sandwich interactions is similar to that of 2 and is approximately reproduced by DFT calculations for the model complex ions {(μ-bpym)[Cu(EMe2Ph)2]2}2+, E = P or As. In contrast, the dinuclear {(μ-bpym)[Cu(P(3-Me-C6H4)3)2]2}(BF4)2 (3) displays a distinctly less distorted metal coordination geometry due to the steric requirements of the methyl groups in the meta-tolyl substituents. The electrochemical reduction of 1 is less reversible than for the phosphine analogues; the one-electron-reduced form 1 • - exhibits a broad, unresolved EPR signal at g = 2.0023. Resonance Raman spectroscopy of 1 shows the typical vibrations of the bpym ligand in agreement with the MLCT assignment of the long-wavelength transitions below 500 nm. All three dinuclear complexes exhibit luminescence at room temperature in the solid and in solution.