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4.
Mechanistic study of oxidation of primary alcohols by Quinolinium
Fluorochromate using micro-amount of chloro-complex of Ir(III) as a
homogeneous catalyst in acidic medium
Sheila Srivastava* and Parul Srivastava
Chemical Laboratories, Feroze Gandhi College, Rae Bareli(U.P.)-229001
,India, Tel. +91-9305034934, Fax-+91-535-270-2720
E-mail:
she_ila72@yahoo.com; parul_9880@yahoo.com
Abstract:
The mechanistic study of iridium(III) catalyzed oxidation of
n-hexanol and n-heptanol (primary alcohols) has been studied
by quinolinium fluorochromate (QFC) in aqueous perchloric
acid medium at 308 K. The reaction followed zero order
kinetics with respect to [primary alcohols]. First-order
kinetics with respect to [QFC] and [Ir(III)] were observed
for the oxidation of primary alcohols. The rate of reaction
decreased with increasing [Cl-]. The variation of
[H+] and ionic strength of the medium had no
significant effect on the rate of the reaction. The values
of rate constants observed at four different temperatures
were utilized to calculate the activation parameters. The
reaction between QFC and primary alcohols, in acidic medium,
exhibits 1:1 stoichiometry. A plausible mechanism conforming
to the kinetic results has been proposed.
KEYWORDS: Mechanistic; Oxidation; Ir(III)
catalyst; Acidic quinolinium fluorochromate; Primary
alcohols.
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