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Unexpected behaviour of copper(I) towards a tridentate Schiff base: Synthesis, structure and properties of new Cu(I)-Cu(II) and Cu(II) complexes

Abstract : The reaction of CuBr with 2,6-bis[1-(2,6-diisopropylphenylimino)ethyl]pyridine L afforded a new Cu(I)-Cu(II) derivative [CuBrL]2[Cu2Br4] (1), while the reaction of [Cu(CH3CN)4]PF6 with L in THF yielded the new Cu(I) compound CuL(THF)(CH3CN)PF6 (2). Derivative 2 further reacted with halogenated solvents to yield halogeno-Cu(II) salts, [CuClL]PF6 (3) using CHCl3 and [CuBrL]Br3 (4) using CHBr3. Compounds 1, 3 and 4 have been fully characterised by X-ray crystallography; they contain essentially similar [CuXL]+ cations with a square planar copper(II) co-ordination. However, the structure of compound 1 must be viewed as built of tetranuclear units since two [CuIIBrL]+ cations are bridged by a [Cu2IBr4]2- anion with a rather strong CuII···Br (2.689(2) Å) secondary interaction. These secondary interactions (CuII cation···FPF5 or Br anion) are weaker in 3 and 4. The electrochemical properties of compounds 1-4 are discussed, too. © 2001 Elsevier Science B.V. All rights reserved.
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Submitted on : Wednesday, April 18, 2018 - 4:15:52 PM
Last modification on : Tuesday, December 10, 2019 - 5:30:08 PM

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B. Le Gall, Françoise Conan, Nathalie Cosquer, J.-M. Kerbaol, M.M. Kubicki, et al.. Unexpected behaviour of copper(I) towards a tridentate Schiff base: Synthesis, structure and properties of new Cu(I)-Cu(II) and Cu(II) complexes. Inorganica Chimica Acta, Elsevier, 2001, 324 (1-2), pp.300-308. ⟨10.1016/S0020-1693(01)00663-6⟩. ⟨hal-01770135⟩

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