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Structural, Magnetochemical and Electrochemical Studies of Dinuclear Complexes Containing the [V V O] 2 , [V IV O] 2 , Cr III 2 , Mn III 2 and Fe III 2 Cores of a Potentially Pentadentate Phenol‐Containing Ligand with (O,N,O,N,O)‐Donor Atoms
Author(s) -
Mukherjee Soumen,
Weyhermüller Thomas,
Bothe Eberhard,
Chaudhuri Phalguni
Publication year - 2003
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200200594
Subject(s) - chemistry , ligand (biochemistry) , electrochemistry , denticity , crystallography , magnetic susceptibility , metal , antiferromagnetism , manganese , bridging ligand , stereochemistry , crystal structure , biochemistry , physics , receptor , organic chemistry , electrode , condensed matter physics
Dinuclear complexes [L 2 Fe III 2 ] ( 1 ), [L 2 Mn III 2 ] ( 2a ), [L 2 Mn III 2 (THF) 2 ] ( 2b ), [L 2 Cr III 2 ] ( 3 ), [L(V IV O) 2 (OCHMe 2 )] ( 4 ) and [L 2 (V V O) 2 ] ( 5 ) with a pentadentate phenol‐containing ligand H 3 L (= C 6 H 2 (CH 3 )(OH){[C(CH 3 ) 3 ] 2 (OH)NCH} 2 ) bearing the N 2 O 3 donor atoms have been synthesized and the X‐ray structures of 1 , 2b , 4 and 5 are reported. The compounds were characterized by IR, UV/Vis and Mössbauer spectroscopy, mass spectrometry, electrochemical and variable‐temperature (2−295 K) magnetic susceptibility measurements. Analysis of the susceptibility data demonstrates antiferromagnetic interactions between the metal centers establishing diamagnetic ground states for complexes 1−4 . The electrochemical results suggest the generation of ligand‐centered oxidation processes attributable to the phenoxyl radicals, rather than the formation of unusually high oxidation states at the central metal centers. The ligand H 3 L has the potential to act in a multidentate fashion as evidenced by the X‐ray structures of 2b and 5 . In compound 2b the central phenolate oxygen of the p ‐cresol ring does not function as a bridging atom between two manganese centers, whereas in 5 the ligand is tetradentate with one noncoordinating nitrogen atom. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)