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Synthesis and Structural Study of Tetravalent (Zr 4+ , Hf 4+ , Ce 4+ , Th 4+ , U 4+ ) Metal Complexes with Cyclic Hydroxamic Acids
Author(s) -
Jewula Pawel,
Berthet JeanClaude,
Chambron JeanClaude,
Rousselin Yoann,
Thuéry Pierre,
Meyer Michel
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201403206
Subject(s) - chemistry , denticity , cerium , actinide , lanthanide , chelation , metal , dodecahedron , thorium , zirconium , crystallography , stereochemistry , ring (chemistry) , transition metal , inorganic chemistry , crystal structure , uranium , materials science , organic chemistry , ion , metallurgy , catalysis
Six‐ and seven‐membered cyclic hydroxamic acids, such as 1‐hydroxypiperidine‐2‐one ( 1 H, 1,2‐PIPOH) and 1‐hydroxyazepan‐2‐one ( 2 H), have recently been identified in some mixed siderophores as one of their three chelating subunits. Compared to their ubiquitous noncyclic counterparts, cyclic hydroxamates are preorganized for metal binding. Surprisingly, the coordination chemistry of these bidentate, monoanionic ligands remains virtually unknown, even in the case of iron(III). We report herein the first structural study of the complexes of 1 – and of 6 – , an unsaturated seven‐membered ring analog of 2 – , with tetravalent cations of transition metals (zirconium and hafnium), lanthanide (cerium), and actinides (thorium and uranium). Structural characterization by means of X‐ray crystallography of the corresponding ML 4 complexes evidenced distorted square antiprismatic coordination geometries with the exception of U 4+ , which favors a dodecahedral arrangement.