Premium
Redox‐Induced μ‐Acetato and μ‐Oxo Core Interconversions in Dinuclear Manganese Tris(2‐methylpyridyl)amine (tpa) Complexes: Isolation and Characterization of [Mn 2 III (μ‐O)(μ‐O 2 CCH 3 )(tpa) 2 ] 3+
Author(s) -
Collomb MarieNoëlle,
Mantel Claire,
Romain Sophie,
Duboc Carole,
Leprêtre JeanClaude,
Pécaut Jacques,
Deronzier Alain
Publication year - 2007
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.200601089
Subject(s) - chemistry , amine gas treating , tris , electrochemistry , monoclinic crystal system , manganese , redox , crystal structure , medicinal chemistry , stereochemistry , ligand (biochemistry) , crystallography , inorganic chemistry , organic chemistry , biochemistry , electrode , receptor
The electrochemical properties of the bis(μ‐acetato) complex [Mn 2 II (O 2 CCH 3 ) 2 (tpa) 2 ] 2+ ( 1 2+ ) [tpa = tris(2‐methylpyridyl)amine] in an organic medium (CH 3 CN) have been studied. Two successive controlled potential oxidations of a solution of 1 2+ at 0.7 and 1.1 V vs. Ag/Ag + (10 m M ) allow the selective and nearly quantitative formation of the mono‐(μ‐oxo) mono‐(μ‐acetato) complex [Mn 2 III (O)(O 2 CCH 3 )(tpa) 2 ] 3+ ( 2 3+ ) and the bis(μ‐oxo) complex [Mn 2 IV (O) 2 (tpa) 2 ] 4+ ( 3 4+ ), respectively. These results show that each substitution of an acetate group by an oxo group is caused by an overall two‐electron oxidation of the corresponding dimanganese complex. The associated electrochemical back transformations were also investigated. Complex 2 3+ , which possesses a rare mono‐(μ‐oxo) mono‐(μ‐acetato) motif, has been isolated and characterized by X‐ray crystallography. This complex crystallizes in the monoclinic system, space group P 2 1 / n with a = 11.9899(17), b = 35.050(5), c = 12.3952(18) Å, β = 101.218(6)°, Z = 4. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)