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Kinetics and mechanism of acetylacetonate transfer from acetylacetonatomanganese(III) to iron(III) in acetonitrile catalysis and inhibition effects
Author(s) -
Schmid Roland,
Sapunov Valentin N.
Publication year - 1979
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550110102
Subject(s) - chemistry , acetonitrile , manganese , catalysis , perchlorate , yield (engineering) , inorganic chemistry , ligand (biochemistry) , dimethylformamide , kinetics , acetylacetone , reaction mechanism , medicinal chemistry , organic chemistry , solvent , ion , biochemistry , materials science , receptor , physics , quantum mechanics , metallurgy
The reaction between tris(acetylacetonato)magnanese(III) and hexa( N , N ‐dimethylformamide)iron(III) perchlorate in acetonitrile proceeds in two stages. The first stage corresponds to the reaction of pentacoordinated Fe(DMF) 5 3+with Mn(acac) 3 , and the rate‐determining step of the second stage consists mainly in the elimination of a DMF ligand from Fe(DMF) 6 3+to yield Fe(DMF) 5 3+which reacts rapidly with the manganese complex. The formation of Fe(DMF) 5 3+is catalyzed by Mn(acac) 3 , this catalytic effect being decreased by manganese products. The rate‐determining step for the formation of Fe(acac) 3 is the transfer of the first acetylacetonate to yield Fe(acac) 2+ . The final products of iron depend on the ratio of reactant concentrations. With Mn or Fe in excess, Fe(acac) 3 or Fe(acac) 2+ are mainly produced.