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H
2
O
2
+
H
2
O
2
MbFe
III
R
2
N=O
H
2
O
MbFe
IV
=O
O
2
−
R
2
NO
MbFe
IV
=O
+
R
2
N=O
R
2
NO
H
2
O
2
O
2
−
Scheme 17.3
Recycling of nitroxide in the MbFe
III
/H
2
O
2
system
O
2
−
M
n
+
O
2
−
H
2
O
R
2
NO
H
2
O
2
1e
−
+
M
(n
+
1)
+
O
2
R
2
N=O
R
2
N
OH
H
2
O
2
2e
−
NADH
NAD
+
Scheme 17.4
Recycling of nitroxide in the presence of biologically relevant oxidants and reductants
(iii) Reduction of the oxoammonium cation and oxidation of the hydroxylamine to the parent nitroxide
via comproportionation (Equation 17.9).
62-64
R
2
N
+
=
H
+
2R
2
NO
•
O
+
R
2
NOH
+
(17.9)
The rate of Equation 17.9 is pH dependent, increasing with the pH since the fastest reaction of
the oxoammonium cation is with the deprotonated form of the hydroxylamine.
64
In the case of
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