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Geometrical and Electronic Structures of Dinuclear Complex Ions (μ-bpym)[Cu(EAr3)2]22+ with Intramolecular \dqOrganic Sandwich\dq Formation (E = P or As; Ar = Aryl; bpym = 2,2'-Bipyrimidine)

, , , , , , , , and . Inorganic Chemistry, 44 (13): 4637--4643 (2005)
DOI: 10.1021/ic050207z

Abstract

(μ-Bpym)[Cu(AsPh3)2]2(BF4)2 (1) was prepd. and studied in comparison with the triphenylphosphine analog (2). Qual., 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 approx. reproduced by DFT calcns. for the model complex ions (μ-bpym)[Cu(EMe2Ph)2]22+, 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 Me groups in the meta-tolyl substituents. The electrochem. redn. of 1 is less reversible than for the phosphine analogs; the 1-electron-reduced form 1.bul.- 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 \textless500 nm. All three dinuclear complexes exhibit luminescence at room temp. in the solid and in soln. [on SciFinder(R)]

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