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Inne
A systematic exploration of nickel(II)/acetate/Di-2-pyridyl ketone chemistry: neutral and cationic tetranuclear clusters, and a novel mononuclear complex.
Autorzy
Rok wydania
2006
Czasopismo
European Journal of Inorganic Chemistry
Strony
2236-2252
DOI
10.1002/ejic.200500898
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
Abstract
The further use of di-2-pyridyl ketone [(2-py)2CO] innickel(II) acetate chemistry has been investigated. Various synthetic procedures have led to the synthesis ofcomplexes [Ni4(O2CMe)2{(2-py)2C(OH)O}4(H2O)2](ClO4)2 (1), [Ni(O2CMe){(2-py)2C(OH)2}{(2-py)2CO}](ClO4)·H2O (2·H2O), [Ni4(O2CMe)3{(2-py)2C(OH)O}4](ClO4)·2H2O·2EtOH (3·2H2O·2EtOH), [Ni4(O2CMe)4{(2-py)2C(OH)O}4]·2MeCN (4·2MeCN), and [Ni4(O2CMe)3{(2-py)2C(OH)O}4](O2CMe)·6H2O·MeCN (5·6H2O·MeCN). The NiII-mediated hydrolysis of (2-py)2CO to give the coordinated molecule (2-py)2C(OH)2 or the monoanion (2-py)2C(OH)O– involves nucleophilic attack by H2O on the carbonyl group. The NiII ion in 2·H2O is coordinated by one monodentate acetate, one N,N′,O-tridentate chelating (2-py)2C(OH)2 molecule, and one N,N′-bidentate chelating (2-py)2CO ligand. The tetranuclear cluster cation of 1 has a cubane {Ni4(μ3-OR)4}4+ core with NiII ions and deprotonated oxygen atoms occupying alternate vertices. The [Ni4(O2CMe)3{(2-py)2C(OH)O}4]+ cations present in the complexes 3·2H2O·2EtOH and 5·6H2O·MeCN have almost identical cubane structures that are different from the structure of the cation of 1. The four metal ions in the centrosymmetric molecules of 4·2MeCN are located at four vertices of a defect dicubane (with two missing vertices) and are bridged by six oxygen atoms. Characteristic IR bands are discussed in terms of the known structures of 1–5. The magnetic data for the NiII cubane 1 has been modeled with two Jvalues, and shows that the coupling consists of two ferromagnetically coupled pairs that are antiferromagnetically coupled to give a diamagnetic ground state. The magneticproperties of 4 have been modeled with three J values, andreveal competing antiferromagnetic and ferromagneticcoupling between the four NiII ions.
Słowa kluczowe
Acetate ligands, Di-2-pyridyl ketone, Magnetic properties, Nickel (II) cubanes, Nickel (II) defect dicubanes, X-ray diffractions
Adres publiczny
https://doi.org/10.1002/ejic.200500898
Strona internetowa wydawcy
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