Journal
DALTON TRANSACTIONS
Volume 43, Issue 45, Pages 16992-16995Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c4dt02327g
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- University of Illinois at Urbana-Champaign
- NSF
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The synthesis of a novel dipodal ligand framework, H-2[N-Me(pi(Cy))(2)], is summarized. Upon metalation with MCl2 salts (M = Fe, Cu), the ligand undergoes a conformational change, resulting in the formation of a trigonal bipyramidal metal center with a pseudoplanar, meridionally-bound ligand framework. This tautomerization positions pendant amines in the metal's secondary coordination sphere. Metalation with M(OTf)(2) in coordinating solvent yields octahedral metal complexes, where two solvent molecules bind in the apical positions with one outer sphere counter ion. Reactivity of these complexes, (N-Me(afa(Cy))(2)) M(X)(2) (X = Cl, OTf), with 2,2'-bypyridine results in ligand reorganization, yielding a facial coordination geometry of the dipodal framework. The described complexes have been characterized by H-1 NMR, EPR, IR, Mossbauer and electronic absorption spectroscopies as well as X-ray crystallography.
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