Heterobimetallic [mu]-Oxido Complexes Containing Discrete V super(V)-O-M super(III)(M = Mn, Fe) Cores: Targeted Synthesis, Structural Characterization, and Redox Studies

Heterobimetallic compounds containing a discrete unsupported VV-O-MIII bridge have been synthesized through a targeted synthesis route. In the V-O-Mn-type complexes, the vanadium (V) centers have a square-pyramidal geometry, completed by a dithiocarbazate-based tridentate Schiff-base ligand, while t...

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Bibliographic Details
Published in:Inorganic chemistry 2014-08, Vol.53 (16), p.8287-8297
Main Authors: Bhattacharya, Kisholoy, Abtab, Sk Towsif, Majee, Mithun Chandra, Endo, Akira, Chaudhury, Muktimoy
Format: Article
Language:English
Subjects:
Bridges (structures)
Diffraction
Iron
Ligands
Manganese
NMR spectroscopy
Synthesis
X-rays
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Summary:Heterobimetallic compounds containing a discrete unsupported VV-O-MIII bridge have been synthesized through a targeted synthesis route. In the V-O-Mn-type complexes, the vanadium (V) centers have a square-pyramidal geometry, completed by a dithiocarbazate-based tridentate Schiff-base ligand, while the manganese (III) centers have either a square-pyramidal (1 and 3) or an octahedral geometry, made up of a Salen-type tetradentate ligand (H2L) as established by X-ray diffraction analysis. The X-ray data also confirm the V-O-M canonical form to contribute predominantly on the overall V-O-M bridge structure. The molecules in solution also retain their heterobinuclear composition, as established by electrospray ionization mass spectrometry and 51V NMR spectroscopy. The iron (III) compounds (6 and 7), on the other hand, show at least four irreversible processes, appearing at Epc = -0.20, -1.0, -1.58, and -1.68 V in compound 6, together with a reversible process (process VIII) at E1/2 = -1.80 V.
ISSN:0020-1669
DOI:10.1021/ic501563r