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Issue 40, 2013
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Novel mixed-valence Cu compounds formed by CuII dimers with double oximato bridges: in situ formation of anionic layer [Cu2(SCN)3]nn

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Abstract

Two new N3O donor ketoxime Schiff bases (HL1 and HL2) have been synthesized by condensing N,N-dimethylethylenediamine with diacetylmonoxime and benzilmonoxime, respectively in a 1 : 1 ratio. Reaction of Cu(ClO4)2·6H2O with HL1 resulted in a discrete oximato-bridged dinuclear CuII complex [Cu2(L1)2(H2O)2](ClO4)2 (1). The same reaction in presence of NaSCN affords the complex {[CuII2(L1)2][CuI41,3-SCN)41,1,3-SCN)2]}n (2), where partial CuII→CuI reduction is observed. In 2, arrays of [CuII2(L1)2]2+ cationic units are inserted in between 2D {[CuI4(SCN)6]2−}n layers and connected via μ1,1,3-SCN links, thus forming a 3D network. On the other hand, reaction of Cu(CH3COO)2 and HL2 in the presence of NaSCN gave rise to a mixed-valence pentanuclear cluster {[CuII2(L2)2(NCS)]2[CuI(SCN)(μ1,1-SCN)(μ1,3-SCN)]} (3) where CuII is also partly reduced to CuI. In compound 3, two cationic [CuII2(L2)2(NCS)]+ units are bridged by the anionic [CuI(SCN)3]2− unit through long Cu–SCN linkages. The ligands and the complexes have been characterized by elemental analysis, UV/Vis and IR spectroscopy. The complexes are further characterized by single crystal X-ray diffraction and variable temperature magnetic (VTM) studies. Finally a complete magneto-structural correlation has been established between compounds 1–3 and all the characterized Cu dimers with a double NO bridge.

Graphical abstract: Novel mixed-valence Cu compounds formed by Cuii dimers with double oximato bridges: in situ formation of anionic layer [Cu2(SCN)3]nn−

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Publication details

The article was received on 13 Jun 2013, accepted on 22 Jul 2013 and first published on 25 Jul 2013


Article type: Paper
DOI: 10.1039/C3DT51561C
Citation: Dalton Trans., 2013,42, 14545-14555
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    Novel mixed-valence Cu compounds formed by CuII dimers with double oximato bridges: in situ formation of anionic layer [Cu2(SCN)3]nn

    P. Dhal, M. Nandy, D. Sadhukhan, E. Zangrando, G. Pilet, C. J. Gómez-García and S. Mitra, Dalton Trans., 2013, 42, 14545
    DOI: 10.1039/C3DT51561C

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