Iron catalysed assembly of an asymmetric mixed-ligand triple helicate

The 2-pyridinecarbaldehyde isonicotinoyl hydrazone (HPCIH) family of ligands are typically tridentate N,N,O chelators that exhibit very high in vitro activity in mobilizing intracellular Fe and are promising candidates for the treatment of Fe overload diseases. Complexation of ferrous perchlorate wi...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2004-10 (20), p.3342-3346
Main Authors: Bernhardt, Paul V, Chin, Piao, Richardson, Des R
Format: Article
Language:English
Subjects:
Catalysis
Crystallography, X-Ray
Ferrous Compounds - chemistry
Hydrazines - chemistry
Hydrazones - chemistry
Iron - chemistry
Iron Chelating Agents - chemistry
Pyridines - chemistry
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Summary:The 2-pyridinecarbaldehyde isonicotinoyl hydrazone (HPCIH) family of ligands are typically tridentate N,N,O chelators that exhibit very high in vitro activity in mobilizing intracellular Fe and are promising candidates for the treatment of Fe overload diseases. Complexation of ferrous perchlorate with HPCIH in MeCN solution gives the expected six-coordinate complex Fe(II)(PCIH)(2). However, complexation of Fe(II) with 2-pyridinecarbaldehyde picolinoyl hydrazone (HPCPH, an isomer of HPCIH) under the same conditions leads to spontaneous assembly of an unprecedented asymmetric, mixed-ligand dinuclear triple helical complex Fe(II)(2)(PCPH)(2)(PPH), where PPH(2-) is the dianion of bis(picolinoyl)hydrazine. The X-ray crystal structure of this complex shows that each ligand binds simultaneously to both metal centres in a bidentate fashion. The dinuclear complex exhibits two well separated and totally reversible Fe(III/II) redox couples as shown by cyclic voltammetry in MeCN solution.
ISSN:1477-9226
1477-9234
DOI:10.1039/b408781j