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Oxovanadium(IV)‐Salen Ion Catalyzed H 2 O 2 Oxidation of Tertiary Amines to N ‐Oxides– Critical Role of Acetate Ion as External Axial Ligand
Author(s) -
Mathavan Alagarsamy,
Ramdass Arumugam,
Ramachandran Mohanraj,
Rajagopal Seenivasan
Publication year - 2015
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.20910
Subject(s) - chemistry , yield (engineering) , medicinal chemistry , substituent , ligand (biochemistry) , substrate (aquarium) , vanadium , catalysis , bond cleavage , oxidation state , ion , inorganic chemistry , photochemistry , organic chemistry , biochemistry , materials science , receptor , oceanography , metallurgy , geology
The oxovanadium(IV)‐salen ion catalyzed H 2 O 2 oxidation of N , N ‐dimethylaniline forms N ‐oxide as the product of the reaction. The reaction follows Michaelis–Menten kinetics and the rate of the reaction is accelerated by electron donating groups present in the substrate as well as in the salen ligand. This peculiar substituent effect is accounted for in terms of rate determining bond formation between peroxo bond of the oxidant and the N‐atom of the substrate in the transition state. Trichloroacetic acid (TCA) shifts the λ max value of the oxidant to the red region and catalyzes reaction enormously. The cleavage of NO bond by vanadium complex leads to moderate yield of the product. But the percentage yield of the product becomes excellent in the presence of TCA.