Synthetic Models for Non-Heme Carboxylate-Bridged Diiron Metalloproteins:  Strategies and Tactics

3,5-Diamino-4H-1,2,4-triazol-1-ium (6-carboxypyridine-2-carboxylato)(pyridine-2,6-dicarboxylato)cuprate(II) trihydrate

“…The study of the construction of metal organic frameworks indicates that under suitable conditions, the transfer of the acidic protons to appropriate bases will result in increased intermolecular interactions and as a result enhanced stabilization of the resulting system (Aghajani et al, 2009). The study of metal carboxylates has always been fascinating for the researchers because they play important roles not only in synthetic chemistry, considering the vast array of coordination modes of the carboxylate group, but also in biological activities (Tshuva et al, 2004;Kuzelka et al, 2003) and physiological effects (Aghabozorg et al, 2007). In our ongoing research to study the packing features of molecules containing metal chelate and triazole rings, the title Cu complex (I) was prepared from 3,5-diamino-1,2,4-triazole and dipicolinic acid.…”

“…For general background to and applications of supramolecular arrangements, see: Lehn (1995); Aghajani et al (2009) ;Tshuva & Lippard (2004); Kuzelka et al (2003). For crystal structures of related complexes, see: Aghabozorg et al (2007); Ramos Silva et al (2008); Wang et al (2004); MacDonald et al (2004).…”

Synthesis, Characterization, and Preliminary Oxygenation Studies of Benzyl- and Ethyl-Substituted Pyridine Ligands of Carboxylate-Rich Diiron(II) Complexes

“…15,16 The introduction of m-terphenyl-based carboxylates, depicted in Chart 1, has facilitated the assembly of the desired dinuclear cores. [16][17][18][19][20] The protective pocket of aromatic rings prevents bimolecular decomposition reactions but can also block access of substrate to the O 2 -activated diiron center. To address this concern, substrates have been incorporated into the ancillary Ndonor ligands coordinated to the iron atoms, as illustrated by the formation of benzaldehyde from a benzyl moiety following exposure to O 2 In the present study we have expanded the family of substrate-tethered carboxylate-bridged diiron(II) compounds having benzyl-or ethyl-derivatized pyridine or aniline donor auxiliary ligands.…”

Oxygen Dissociation by Concerted Action of Di-Iron Centers in Metal–Organic Coordination Networks at Surfaces: Modeling Non-Heme Iron Enzymes

“…This mechanism displays a cooperative catalytic action of the Fe ions, is ratelimited by the first O 2 dissociation, and exploits the structure of the dinuclear site. Since the di-iron MOCN displays carboxylate ligand shifts analogous to that exhibited by synthetic biomimetic systems 22,32,33 and biological metalloenzymes sensitive to dioxygen, 47 ' REFERENCES…”

“…20,21 Fundamental insight into the active site functionality has been achieved by focusing on simpler synthetic systems that model elementary sites of biological units. 22 One successful class of such model systems is based on sterically hindered carboxylic acids capable to stabilize di-iron(II) complexes. These are shown to react in solution with O 2 and to display characteristic ligand ABSTRACT: The high chemical reactivity of unsaturated metal sites is a key factor for the development of novel devices with applications in sensor engineering and catalysis.…”