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Issue 12, 2017
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NiII formate complexes with bi- and tridentate nitrogen-donor ligands: synthesis, characterization, and magnetic and thermal properties

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Abstract

The synthesis of four NiII formate complexes of the type [Ni(NN)n][O2CH]2 (2, adduct with 3/4 EtOH, NN = en, [e with combining low line]thyle[n with combining low line]ediamine, n = 3; 4, NN = dien, N,N′,N′′-[d with combining low line][i with combining low line][e with combining low line]thyle[n with combining low line]etriamine, n = 2), [Ni2(O2CH)4(H2O)(tmeda)2] (3, tmeda = N,N,N′,N′-[t with combining low line]etra[m with combining low line]ethyl[e with combining low line]thylene[d with combining low line]i[a with combining low line]mine) and [{Ni(O2CH)2(pmdta)}2·H2O] (5, pmdta = N,N′,N′,N′′,N′′-[p with combining low line]enta[m with combining low line]ethyl[d with combining low line]iethylene[t with combining low line]ri[a with combining low line]mine) by a reaction of [{Ni(O2CH)2}·2H2O] (1) with the respective N-donor bases is reported. The structures of 2–5 in the solid state were determined by single X-ray structure analysis, revealing a discrete dinuclear structure of 3 and the formation of polymeric networks in the case of 2, 4 and 5 due to intermolecular hydrogen bonding. SQUID and ESR measurements of 3 evidenced a weak antiferromagnetic coupling between the NiII ions and an easy plane magnetic anisotropy. Accompanying quantum chemical studies of the magnetic properties and IR characteristics of 3 were performed to strengthen the conclusions drawn from experimentally obtained data. The thermal decomposition temperatures of 2–5 were determined by TG (thermogravimetry) and obtained residues were analyzed by PXRD (powder X-ray diffraction) measurements. The decomposition processes were completed at 207 (3), 215 (5), 250 (2) and 273 °C (4) and are shown to result in the formation of pure metallic nickel.

Graphical abstract: NiII formate complexes with bi- and tridentate nitrogen-donor ligands: synthesis, characterization, and magnetic and thermal properties

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Publication details

The article was received on 02 Dec 2016, accepted on 15 Feb 2017 and first published on 07 Mar 2017


Article type: Paper
DOI: 10.1039/C6DT04556A
Citation: Dalton Trans., 2017,46, 3963-3979
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    NiII formate complexes with bi- and tridentate nitrogen-donor ligands: synthesis, characterization, and magnetic and thermal properties

    K. Rühlig, A. Abylaikhan, A. Aliabadi, V. Kataev, S. Liebing, S. Schwalbe, K. Trepte, C. Ludt, J. Kortus, B. Büchner, T. Rüffer and H. Lang, Dalton Trans., 2017, 46, 3963
    DOI: 10.1039/C6DT04556A

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