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Table 4 Kinetic parameters of Co–Co2B nanocomposites in the reduction of the PNP substrate using sodium borohydride as a cosubstratea
E (M)
KM (mM)
Vmax (mM min21
)
Kcat (s21
5.2 6 104
)
Kcat/KM (M21 s21
4.4 6 106
)
2.3 6 10211
11.83
14 468
a
[E] is the nanoparticle molar concentration of Co–Co2B nanocomposites,20 KM is the Michaelis constant, Vmax is the maximal reaction
velocity, Kcat is the catalytic constant, where Kcat = Vmax/[E] and Kcat/KM is the catalyst efficiency.
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Conclusion
In conclusion, we have developed a cost effective, efficient
reduction procedure to convert an aromatic nitro group to
amine using simple first row transition metal Co–Co2B
nanocomposites. The reaction proceeds under mild and
ambient conditions employing sodium borohydride in aqu-
eous medium or employing hydrazine, without affecting other
functionalities such as acid, halo, hydroxyl, ester, and
benzyloxy groups. The catalyst is also useful in the reduction
of an oxime group. In addition to the reduction of the aromatic
nitro group, the sodium borohydride system also reduces
nitrile functionality, which is not observed in the hydrazine
system, leading to chemoselectivity. Another interesting
chemoselectivity was observed during the reduction studies
of 4-allyloxy nitrobenzene. The sodium borohydride system
resulted in the selective reduction of the double bond, while
the hydrazine system selectively reduced the nitro group
witnessing a chemoselective switch of the hydrogen source for
the present reduction protocol. The rapid reduction of
nitrophenol using aqueous sodium borohydride may find
application in developing a waste water treatment process to
get rid of nitrophenols from industrial and agricultural waste.
The added feature of the present method is the ease of
separation of the nanocatalyst after use by an external magnet
and the recyclability of the catalyst for several cycles without
apparent leaching. We have also shown for the first time that
the nanocatalyst follows nitroreductase enzyme-like kinetics
with a very high Kcat/KM value, approaching the state of
catalytic perfection.
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