Heterometallic CuII FeIII and CuII MnIII alkoxo-bridged complexes revealing a rare hexanuclear M6 (μ-X)7 (μ3 -X)2 molecular core

Dalton Transactions : an International Journal of Inorganic Chemistry
Oksana V NesterovaArmando J L Pombeiro

Abstract

The novel hexanuclear complexes [Cu4Fe2(OH)(Piv)4(tBuDea)4Cl]·0.5CH3CN (1) and [Cu4Mn2(OH)(Piv)4(tBuDea)4Cl] (2) were prepared through one-pot self-assembly reactions of copper powder and iron(ii) or manganese(ii) chloride with N-tert-butyldiethanolamine (H2tBuDea) and pivalic acid (HPiv) in acetonitrile. Crystallographic studies revealed the uncommon molecular core type M6(μ-X)7(μ3-X)2 in 1 and 2, which can be viewed as a combination of two trimetallic M3(μ-X)2(μ3-X) fragments joined by three bridging atoms. The analysis and classification of the hexanuclear complexes having a M3(μ-X)2(μ3-X) moiety as a core forming fragment using data from the Cambridge Structural Database (CSD) were performed. Variable-temperature (1.8-300 K) magnetic susceptibility measurements of 1 showed a decrease of the effective magnetic moment value at low temperature, indicative of antiferromagnetic coupling between the magnetic centres (JFe-Cu/hc = -6.9 cm-1, JCu-Cu/hc = -4.1 cm-1, JFe-Fe/hc = -24.2 cm-1). Complex 1 acts as a catalyst in the reaction of mild oxidation of cyclohexane with H2O2, showing the yields of products, cyclohexanol and cyclohexanone, up to 17% using pyrazinecarboxylic acid as a promoter. In the oxidation of cis-1,2-dimethylcyc...Continue Reading

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Citations

Mar 25, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Oksana V NesterovaDmytro S Nesterov
Sep 29, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Nuno Reis ConceiçãoDmytro S Nesterov

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Methods Mentioned

BETA
X-ray
amidation
PCA

Software Mentioned

SHELXL

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