Structures and Magnetic Properties of Tetranuclear Nickel(II) Complexes with Unusual μ3‐1,1,3 Azido Bridges

F Meyer, S Demeshko, G Leibeling… - … A European Journal, 2005 - Wiley Online Library
F Meyer, S Demeshko, G Leibeling, B Kersting, E Kaifer, H Pritzkow
Chemistry–A European Journal, 2005Wiley Online Library
Pyrazolate‐based dinucleating ligands with thioether‐containing chelate arms have been
used for the synthesis of a family of novel tetranuclear nickel (ii) complexes [L2Ni4 (N3) 3
(O2CR)](ClO4) 2 that incorporate three azido bridges and one carboxylate (R= Me, Ph).
Molecular structures have been elucidated by X‐ray crystallography in four cases, revealing
Ni4 cores with a unique topology in which two of the azido ligands adopt an unusual μ3‐1,
1, 3 bridging mode. The compounds were further characterized by mass spectrometry, IR …
Abstract
Pyrazolate‐based dinucleating ligands with thioether‐containing chelate arms have been used for the synthesis of a family of novel tetranuclear nickel(II) complexes [L2Ni4(N3)3(O2CR)](ClO4)2 that incorporate three azido bridges and one carboxylate (R = Me, Ph). Molecular structures have been elucidated by X‐ray crystallography in four cases, revealing Ni4 cores with a unique topology in which two of the azido ligands adopt an unusual μ3‐1,1,3 bridging mode. The compounds were further characterized by mass spectrometry, IR spectroscopy, and variable‐temperature magnetic susceptibility measurements. Magnetic data analyses indicate a combination of significant intramolecular ferromagnetic and antiferromagnetic exchange interactions that give rise to an overall ST = 0 ground state. The sign and the magnitude of the individual couplings have been rationalized in the framework of the common magnetostructural correlations for end‐to‐end and end‐on azido linkages, suggesting that these correlations also remain valid for the respective fragments of multiply bridging μ3‐1,1,3 azido ligands.
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