Iron(III)-pivalate-based complexes with tetranuclear {Fe4(?3-O)2}8+ cores and n-donor ligands: formation of cluster and polymeric architectures

Baca, Svetlana G., Filippova, Irina G., Keene, Tony D., Botezat, Olga, Malaestean, Iurii L., Stoeckli-Evans, Helen, Kravtsov, Victor Ch., Chumacov, Iurii, Liu, Shi-Xia and Decurtins, Silvio (2011) Iron(III)-pivalate-based complexes with tetranuclear {Fe4(?3-O)2}8+ cores and n-donor ligands: formation of cluster and polymeric architectures. European Journal of Inorganic Chemistry, 2011 (3), 356-367. (doi:10.1002/ejic.201000838).

Abstract

Different synthetic routes have been used for the preparation of a new tetranuclear [Fe4O2(O2CCMe3)(8)(bpm)] cluster (1) and a one-dimensional coordination polymer [Fe4O2-(O2CCMe3)(8)(hmta)](n) (2) (bpm = 2,2'-bipyrimidine and hmta = hexamethylenetetramine). For cluster 1, two structural isomers, 1a and 1b center dot 3MeCN, have been found. X-ray crystallographic analysis showed that all complexes consist of a central {Fe-4(mu(3)-O)(2)}(8+) core. In 1a, metal ions in the core are additionally linked by six bridging pivalates as two other pivalates and a bpm ligand are chelated to Fe-III ions, whereas in cluster 1b, metal ions in the {Fe-4(mu(3)-O)(2)}(8+) core are linked by seven bridging pivalates and only one carboxylate as well as bpm are chelated to the iron centers. In coordination polymer 2, [Fe4O2(O2CCMe3)(8)] clusters are bridged by hmta ligands to form zigzag chains. Magnetic measurements have been carried out to characterize these complexes and revealed antiferromagnetic interactions between Fe-III ions with best-fit parameters of J(wb) = -72.2 (1a) and -88.7 cm(-1) (1b) for wing...body interactions.

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Contributors

Author: Tony D. Keene

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