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A mononuclear complex and a cubane cluster from the initial use of 2-(hydroxymethyl)pyridine in nickel(II)carboxylate chemistry.
Autorzy
Rok wydania
2009
Czasopismo
Numer woluminu
28
Strony
3373-3381
DOI
10.1016/j.poly.2009.06.049
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
The reactions of 2-(hydromethyl)pyridine, hmpH, with Ni(O2CMe)2·4H2O in H2O, in the absence of counterions, have been investigated. The synthetic study has led to the two new complexes [Ni(O2CMe)2(hmpH)2] (1) and [Ni4(O2CMe)4(hmp)4(H2O)2] (2). Complex 1 can also be transformed into 2 by reacting with an excess of NaOH in H2O. The structures of 1 and 2·2.25H2O·0.5(1,4-dioxane) have been solved by single-crystal, X-ray crystallography. The octahedral NiII center in centrosymmetric 1 is coordinated by two 1.10 (Harris notation) MeCO2− groups and two N,O-chelating (1.11) hpmH ligands. The tetranuclear cluster molecule of 2·2.25H2O·0.5(1,4-dioxane) possesses a distorted cubane {Ni4(μ3-OR′)4}4+ core [R′ = (2-pyridyl)CH2–] with the NiII ions and the oxygen atoms from the 3.31 hmp− ligands occupying alternate vertices of the cube. Two 2.11 MeCO2− groups cap two opposite faces of the cube, while two 1.10 MeCO2− ions and two aqua ligands complete the octahedral coordination sphere of the metal centers. Characteristic IR bands for the two complexes are discussed in terms of the nature of bonding and the structures of the two complexes. The variable-temperature magnetic properties of 2 have been modeled with two J values, and reveal antiferromagnetic exchange interactions between the four NiII ions to give a diamagnetic ground state.
Słowa kluczowe
Acetate ligands, Crystal structures, 2-(Hydroxymethyl)pyridine metal complexes, Magnetic properties, Nickel(II) cubane clusters
Adres publiczny
https://doi.org/10.1016/j.poly.2009.06.049
Strona internetowa wydawcy
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