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Mechanism of Reduction of 2,2‐Dibromomethyl‐1,3‐propanediol by Ni I ‐Tetraazamacrocyclic Complexes in Aqueous Solution − A Pulse Radiolysis and Electrochemical Study
Author(s) -
Shandalov Elisabetha,
Zilbermann Israel,
Maimon Eric,
Nahmani Yeoshua,
Cohen Haim,
Adar Eilon,
Meyerstein Dan
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.200300114
Subject(s) - chemistry , radiolysis , aqueous solution , electrochemistry , reaction rate constant , catalysis , kinetics , inorganic chemistry , nickel , propanediol , electrode , organic chemistry , physics , quantum mechanics
The reduction, catalytic reduction and the electrocatalytic reduction of halo‐organic compounds are of major interest due to their role as pollutants. The mechanism and kinetics of reduction of 2,2‐dibromomethyl‐1,3‐propanediol by several Ni I tetraazamacrocyclic complexes, (Ni I L i ) + (i = 1−4), in aqueous solutions to yield Br − and the non‐halogenated compound was studied using the pulse radiolysis technique. The rate constants k = 5.3 × 10 8 , 1.6 × 10 7 , 6.0 × 10 5 and 3.5 × 10 4 M −1 s −1 for L 1 , L 2 , L 3 and L 4 respectively, of the reactions (Ni I L i ) + + RBr ⇄ (Ni II L i ) 2+ + Br − + R · increase with the free‐energy gain in the reaction. All these complexes are good electrocatalysts for the reduction of this substrate. The mechanisms of the reductions is are discussed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)