Reaction of the nine-nuclear cluster Ni9(HOOCCMe3)4(μ4-ΟΗ)3(μ3-OH)3 (OOCCMe3)12 (1) with pyridine results
in the binuclear species Py4Ni2(OOCCMe3)2(μ-OOCCMe3)2(μ-OH2) (2). Thermolysis of 2 at 100−140 °C in
toluene or xylene leads to complex Py2Ni2(HOOCCMe3)2(OOCCMe3)2(μ-OOCCMe3)2(μ-OH2) (3). This complex
can be converted back in 2 by the reaction of 3 with 2 equiv of pyridine. Thermolysis of solid 3 in vacuo at 170
°C gives the binuclear tetra-bridged trimethylacetate Py2Ni2(μ-OOCCMe3)4 (4) which can be reverted in 3 by
reaction with 1 equiv of H2O and 2 equiv of HOOCCMe3. Compound 4 might be also prepared by the reaction
of the complexs L2Ni2(μ-OOCCMe3)4 (L = 2,3-lutidine (5), Et3N (6)) with pyridine at 40−80 °C in hexane or
benzene solution. Complexes 5 and 6 are formed in an one-step reaction by interaction of complex 1 and ligand
L. Complex Dipy2Ni2(OOCCMe3)2(μ-OOCCMe3)2(μ-OH2) (7), an isoelectronic analogue of complex 2, was
prepared by reacting 1 with Dipy. Thermolysis of solid 7 at 170 °C in vacuo gives monomer DipyNi(OOCCMe3)2
(8). Hetero-ligand complex DipyNi(NH2Ph)(OOCCMe3)2 (9) was obtained upon the reaction of PhNH2 with
complex 7 at 20 °C in benzene or MeCN. Reaction of 1 with α,α‘,α‘ ‘-tripyridyl leads to the formation of the
monomeric TerpyNi(OOCCMe3)2 (10). Complexes 4−10 were characterized with X-ray data. Magnetic properties
of the synthesized complexes are discussed.
The reaction of NiCI 2 9 6H20 with Me3CCOOH and KOH taken in a molar ratio of 1 : 2 : 2 in water afforded the nonanuclear anti.ferromagnetic complex [Nig(Me3CCOOH)4(p4-O)3(I~3-OH)3(OOCCMe3)I2], which apparently contains Ni II and Ni III atoms. The complex was isolated by extraction with CH2C12, benzene, or hexane. The reactions of this complex with pyridine bases (pyridine (Py), 3,4-1utidine (Lut), and nicorandil (Nic)) gave the adducts L4Ni2(OOCCMe3)2(~t-OOCCMe3)2(tt-OH) (L = Py, Lut, or Nic, respectively). According to magnetic measurements, intramolecular ferromagnetic exchange interactions in these adducts are complemented by intermoleeular antiferromagnetic interactions. Pyrolysis of the pyridine adduct in air or under an inert atmosphere in xylene yielded the antiferromagnetie complex Py2Ni2(Me3CCOOH)2(OOCCMe3)2(~t-OOCCMe3)2(~.-OH2), which contains Ni 11 atoms. The structures of all the complexes synthesized were established by X-ray diffraction analysis. The electronic absorption spectra of these compounds are considered.
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