Abstract
Tribochemical reactions of KBr, KI and CaI2 with [Cu(L)Cl2(EtOH)3/2(H2O)]1/2H2O (L = formylhydrazine) give novel CuI and CuII complexes, which have been characterized by elemental analyses, spectral (i.r., u.v.–vis., 1H-n.m.r.) and magnetic measurements. The i.r. spectra indicate that (L) behaves in a monodentate manner, coordinating via the azomethine nitrogen (C-N) group in the CuII complexes, but behaving as a bidentate ligand, via the carbonyl oxygen and NH2 groups in the CuI complexes. KI and CaI2 react with [Cu(L)Cl2(EtOH)3/2(H2O)]-1/2H2O in the solid state, accompanied by a colour change, substitution of the chloride by iodide ions, and reduction of CuII to CuI to give complexes with formulae [Cu(L)I(EtOH)1/2] and [Cu1.7(L)I1.7(EtOH)1/2]. On the other hand, the tribochemical reaction of KBr with [Cu(L)Cl2(EtOH)3/2(H2O)]1/2H2O is accompanied by a colour change; substitution of the chloride by bromide ions, but without reduction of CuII and yields a complex of formula [Cu(L)2Br2(EtOH)(H2O)]1/2EtOH. The spectral and magnetic results suggest a distorted octahedral geometry for the CuII complexes while a tetrahedral geometry around the CuI ion. The non-stoichiometric structure of [Cu1.7(L)I1.7(EtOH)1/2] is discussed.
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Mostafa, M.M., El-Shazly, R.M., Rakha, T.H. et al. The dangers of using KBr, KI and CaI2 as mulling agents during the preparation of infrared discs of complexes. Transition Metal Chemistry 27, 337–340 (2002). https://doi.org/10.1023/A:1014830319501
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DOI: https://doi.org/10.1023/A:1014830319501