1416062-81-1Relevant articles and documents
Syntheses and electronic structure of bimetallic complexes containing a flexible redox-active bridging ligand
Lindsay, Stacey,Lo, Siu K.,Maguire, Oliver R.,Bill, Eckhard,Probert, Michael R.,Sproules, Stephen,Hess, Corinna R.
, p. 898 - 909 (2013/03/13)
The new ligand L1, 1-N,1-N-bis(pyridine-2-ylmethyl)-3-N- (pyridine-2-ylmethylidene)benzene-1,3-diamine, was synthesized as a platform for the study of bimetallic complexes containing redox-active ligands. The asymmetric L1 contains a redox-active α-iminopyridine unit bridged to redox-inert bis(2-pyridylmethyl)amino counterpart and offers two distinct coordination sites. The coordination chemistry of L1 with Fe, Cu, and Zn was examined. Reaction with zinc afforded the asymmetric binuclear complex [(L1)Zn2Cl4] (1), whereas the symmetric [(L1)2Fe2(OTf)2](OTf) 2 (2) and [(L1)2Cu2](OTf) 4 (3) were isolated in reactions with iron and copper. Both metal-and ligand-centered redox processes are available to the series of metal compounds. EPR and Moessbauer spectroscopy and magnetic susceptibility studies establish that both 2 and 3 are paramagnetic; the vanishingly small ferromagnetic interaction produces decoupled high-spin FeII (S = 2) ions in 2. DFT calculations provide further insight into the nature of the exchange interactions in the dimeric systems.
