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Rational Design of the First Closed Coordination Capsule with Octahedral Outer Shape
Author(s) -
Müller Iris M.,
Spillmann Susanne,
Franck Holger,
Pietschnig Rudolf
Publication year - 2004
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200305564
Subject(s) - octahedron , ethylenediamine , chemistry , ligand (biochemistry) , crystallography , crystal structure , stereochemistry , coordination complex , octahedral molecular geometry , chloride , inorganic chemistry , metal , organic chemistry , receptor , biochemistry
The rational synthesis of an octahedral coordination capsule in which the triangular faces are covered by single ligands is described herein. Starting with tris(2‐hydroxybenzylidene)triaminoguanidinium chloride [H 6 L]Cl, we observed an oxidative cyclization of this ligand in the presence of PPh 4 + ions resulting in the complex [Pd(H 2 L′)(PPh 3 )] ( 1 ). The use of 5,5‐diethylbarbiturate (bar 2− ) as a bridging ligand in the presence of [Co(en) 3 ] 3+ (en=ethylenediamine) leads to the formation of a rectangular box with the formula (Et 4 N) 6 [{Co{(PdCl)(Pd)L} 2 (μ‐bar)} 2 ] ( 2 ). The analysis of the architecture of compounds 1 and 2 enables the development of a self‐assembly strategy for the synthesis of an octahedral coordination cage 3 with the formula Na 4 (Et 3 NH) 12 [(Pd 3 L) 8 {μ‐(bar)} 12 ]⋅ x H 2 O. Compound 3 was characterized by 13 C‐MAS‐NMR spectroscopy and single‐crystal structure analysis.