Mild oxidation of hydrocarbons by tert-butyl hydroperoxide catalyzed by electron deficient manganese(III) corroles

Article abstract of DOI:10.1016/j.molcata.2010.09.001

Mild oxidations of alkenes with tert-butylhydroperoxide catalyzed by electron deficient manganese(III) corroles have been achieved at room temperature. The oxygenation of cyclohexane, adamantane and toluene has also been studied under similar reaction conditions. The oxidation has been shown to proceed with participation of alkylperoxy (ROO) radicals and organo-hydroperoxide (ROOH). A reaction mechanism is proposed based on the experimental results.

Full text of DOI:10.1016/j.molcata.2010.09.001

Journal of Molecular Catalysis A: Chemical 332 (2010) 1–6
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Journal of Molecular Catalysis A: Chemical
journal homepage: www.elsevier.com/locate/molcata
Editor’s Choice paper
Mild oxidation of hydrocarbons by tert-butyl hydroperoxide catalyzed by
electron deficient manganese(III) corroles
Suranjana Bose, Anand Pariyar, Achintesh Narayan Biswas, Purak Das, Pinaki Bandyopadhyay∗
Department of Chemistry, University of North Bengal, Raja Rammohunpur, Siliguri 734013, West Bengal, India
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 25 May 2010
Received in revised form 19 August 2010
Accepted 2 September 2010
Available online 15 September 2010
Mild oxidations of alkenes with tert-butylhydroperoxide catalyzed by electron deficient manganese(III)
corroles have been achieved at room temperature. The oxygenation of cyclohexane, adamantane and
toluene has also been studied under similar reaction conditions. The oxidation has been shown to pro-
ceed with participation of alkylperoxy (ROO•) radicals and organo-hydroperoxide (ROOH). A reaction
mechanism is proposed based on the experimental results.
© 2010 Elsevier B.V. All rights reserved.
Keywords:
Manganese corrole
Catalysis
Oxygenation
tert-Butyl hydroperoxide
1. Introduction
the manganese(III) corrole catalyzed oxygenation of hydrocarbons
reported so far are only limited to the oxidation of alkenes [31–35]
The oxygenation of hydrocarbons under mild conditions to more
valuable products remains an area of active interest in chemical sci-
ence. Extensive efforts have been dedicated to develop synthetic
homogeneous catalysts for selective oxygenation of hydrocar-
bons under mild conditions [1–8]. In this direction transition
metal complexes of porphyrins, tetradentate diamine-dipyridine,
phthalocyanines, 1,4,7-triazacyclononane and Schiff bases have
been explored as oxidation catalysts [9–15]. Much effort has been
focused on metalloporphyrins in the search of efficient catalyst
to promote oxygenation of hydrocarbons under mild conditions
[16–18]. Metal complexes of corroles, tetrapyrrolic macrocycle
with one meso carbon short from porphyrin skeleton, are emerg-
ing as an important group of catalysts in recent years [19–34].
Among the metallocorroles, manganese(III) corroles have received
more attention as catalysts in hydrocarbon oxidation [31–34].
Gross and co-workers first demonstrated that manganese(III) com-
plex of 5,10,15-tris(pentafluorophenyl) corrole, [Mn(III) (tpfc)],
catalyzes oxidation of styrene with PhIO [31]. Later the ␤-pyrrole-
halogenated manganese(III) complexes, [F8Mn(III)(tpfc)] [32] and
[Br8 Mn(III)(tpfc)] [33], were used for catalyzing the oxidation of
alkenes by iodosylbenzene and both the complexes emerged as
better catalysts than complex [Mn(III)(tpfc)]. Recently the catalytic
activity of [Mn(III)(tpfc)] in oxidation of styrene with PhIO has been
found to be enhanced by the axial coordination of imidazole [34]. All
but catalytic alkane oxidation by manganese(III) corrole is yet to be
explored. On the other hand, iodosylbenzene has been used as the
only terminal oxidant in oxygenation of hydrocarbons catalyzed by
manganese(III) corrole [31–34]. No report on manganese corrole
catalyzed hydrocarbon oxidation with any mild terminal oxidant
is available in the literature, although hydrogen peroxide has
been employed in asymmetric sulfoxidation catalysed by albumin-
conjugate manganese(III) corrole [35]. Recently manganese(III)
corrole has emerged as an efficient decomposition catalyst for per-
oxynitrite to benign products in vitro and in vivo studies [36–39].
There is no known biological defence system against peroxyni-
trite which is involved in the damage of variety of biomolecules,
specially those are of vital importance for normal cardiovascular
function [40,41]. The mode of catalytic action of amphiphilic man-
ganese(III) corrole on peroxynitrite is disproportionation to nitrite
and molecular oxygen. The substrate acts as two-electron oxidant
of manganese(III) corrole to (oxo)manganese(V) corrole as well
as two-electron reductant of (oxo)manganese(V) species [39]. The
catalytic behaviour of amphiphilic manganese(III) corrole towards
hydrogen peroxide also follows the similar pattern [35]. In this
context it is worthy to investigate the reactivity of manganese(III)
corrole towards alkylhydroperoxide.
Herein we wish to report the catalytic reactivity of a group
of electron deficient manganese(III) corroles in oxidizing alkanes
and alkenes with mild tert-butyl hydroperoxide at room tem-
perature. The present work provides the first ever application of
tert-butyl hydroperoxide as terminal oxidant in manganese(III)
corrole catalyzed hydrocarbon oxygenation reactions. The rate
∗
Corresponding author. Tel.: +91 353 2776381; fax: +91 353 2699001.
E-mail address: pbchem@rediffmail.com (P. Bandyopadhyay).
1381-1169/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.molcata.2010.09.001

2
S. Bose et al. / Journal of Molecular Catalysis A: Chemical 332 (2010) 1–6
constant for the reaction between the Mn(III) corroles and the
tert-butyl hydroperoxide has been measured. A plausible reaction
mechanism has been proposed on the basis of experimental results.
F
1 R1=
2 R1=
, R2= H
R2 R1
R2
F
F
R2
R1
R2
R2
R1
R2
2. Experimental
N
N
N
F
III
Mn
N
F
, R2= H
Acetonitrile and dichloromethane were distilled under argon
from CaH2 and CaCl2 respectively prior to use. Cyclohexene was
distilled under argon to remove the inhibitor and passed through
a silica gel column prior to reaction. Other substrates, all the reac-
tion products, dodecane (internal standard) and t-BuOOH (as ∼70%
solution in water) were purchased from Aldrich and were used
as received. The exact active oxygen content of the oxidant was
determined iodometrically prior to use.
F
F
F
R2
R2
F
3 R1=
F , R2= Br
F
F
Scheme 1. Manganese(III) corrole catalysts used in this study.
2.1. Synthesis of the complexes
The syntheses of the free base corroles, 5,10,15-tris(2,6-
difluorophenyl)corrole (tdfc) and 5,10,15-tris(pentafluorophenyl)
corrole (tpfc) were carried out by using ‘solvent free’ condensa-
tion of pyrrole and the respective aldehydes introduced by Gross
et al. [42]. The complex [Mn(III)(tdfc)] (1) was synthesised from
Mn(OAc)2·4H2O and the corresponding ligand in refluxing DMF
(10 mL) and the green product was purified by preparative TLC on
a silica gel plate using 1:1 dichloromethane/hexane as the eluant.
[Mn(tdfc)] (1): yield: 85%. Anal. Calcd for C37H17N4F6Mn: C,
64.73; H, 2.50; N, 8.16. Found: C, 64.81; H, 2.37; N, 8.25; MS (CI+,
isobutane): m/z (%): 686 (100) [M+]; UV–vis (CH2Cl2): ꢀmax [nm]
(log ε) = 400 (4.55), 416 (4.53), 487 (4.14), 622 (4.01).
products were done from the response factors of standard product
samples.
3. Results and discussion
The catalytic activities of the manganese(III) corroles (1–3)
(Scheme 1) for hydrocarbon oxidation were examined with tert-
butylhydroperoxide at room temperature.
3.1. Catalytic oxidation of alkenes
At room temperature all the three manganese(III) corroles (1–3)
emerge as effective catalysts in oxidizing cyclohexene with mild
tert-butylhydroperoxide (t-BuOOH) under both aerobic and anaer-
obic conditions (Table 1).
The complete oxidation of cyclohexene is achieved within 6 h in
presence of dioxygen, whereas it takes 24 h for complete conver-
sion of the substrate in the absence of dioxygen. The faster reaction
rates in presence of dioxygen clearly suggest the involvement of
dioxygen in the oxygenation process by the present catalytic sys-
tem.
Under both aerobic and anaerobic conditions, allylic oxidation is
favoured and 2-cyclohexen-1-one is the major product along with
2-cyclohexen-1-ol as minor one. In contrast, the oxidation of cyclo-
hexene by catalyst 2 with PhIO is limited to only 11% [33]. The
performance of catalyst 3 in the present oxidizing system is more
selective than its reported performance with PhIO [33].
It is observed that if the reaction mixture is finally treated with
excess PPh3 before the GC analysis, the resulting product pat-
tern drastically differs from that obtained prior to PPh3 addition.
After the reduction, 2-cyclohexen-1-ol becomes the major product
whereas 2-cyclohexen-1-one appears as minor product (Table 1).
Since alkyl hydroperoxides are known to be readily and quantita-
tively reduced by PPh3 to yield the corresponding alcohols [43], the
present results establish the production of cyclohexenyl hydroper-
oxide as an intermediate during the catalytic cycles.
The electron-deficient manganese(III) corrole catalysts (1–3)
have been found to be effective in bringing about oxidation of
styrene under identical reaction condition. In all the cases, ben-
zaldehyde is obtained as the major product together with styrene
oxide and trace amount of phenyl acetaldehyde. Under anaero-
bic condition, yield of styrene oxide is improved indicating the
activation of dioxygen in the present catalytic system. It is note-
worthy that styrene oxide is formed as the major product together
with phenyl acetaldehyde in the reported oxidation of styrene by
manganese(III)corrole/PhIO systems [31–34]. The present results
significantly differ from the product pattern of alkene oxidation by
manganese(III)corrole/PhIO system and point towards the involve-
The complexes [Mn(III)(tpfc)] (2) and [Br8Mn(III)(tpfc)] (3) were
prepared following reported methods [31,33]. The elemental ana-
lytical and spectral data are in agreement with those reported in
the literature [31,33].
2.2. Catalytic experiments
Catalytic reactions were carried out in small screw capped
vials fitted with PTFE septa. In a typical reaction 25 ␮M of cat-
alyst and 200 mM (100 mM in case of adamantane) of substrate
were dissolved in 2 mL of acetonitrile (argon saturated in case of
anaerobic reactions) or 3:2 acetonitrile/dichloromethane in case of
adamantane. The oxidation reaction was initiated by adding 2 mM
of t-BuOOH and the contents were magnetically stirred. After peri-
odic time intervals standard solution of dodecane was added to
this reaction mixture and an aliquot was injected into a capillary
column of a preheated GC.
2.3. Kinetic measurements
In a typical kinetic experiment a cuvette fitted with silicon
rubber septa was degassed by blowing argon over it for 15 min.
Degassed acetonitrile (2 mL) was taken in the cuvette. Micromolar
amount of [Mn(III)(tpfc)] in acetonitrile was treated with millimo-
lar amount of t-BuOOH. The cell was vigorously shaken and was
placed immediately in a thermostatted cell holder in a spectropho-
tometer and the absorbance data at 470 nm were collected at 5-s
intervals. Absorbance vs. time plots have been analyzed in details
in the main body of this paper.
2.4. Product analysis
The product analysis was done by Perkin Elmer Clarus-500 GC
with FID (Elite-I, Polysiloxane, 15-meter column) by injecting 1 ␮L
aliquot from the reaction vial taken after addition of dodecane
as internal standard. The identification and quantification of the

S. Bose et al. / Journal of Molecular Catalysis A: Chemical 332 (2010) 1–6
3
Table 1
Catalytic oxidation of alkenes with t-BuOOH.
Substrate
Catalyst
Atmosphere
Product profile (%)a,b
Cyclohexene oxide
Cyclohexenol
Cyclohexenone
Air
Argon
Air
Argon
Air
Argon
2 [1]
1 [nil]
1 [1]
1 [nil]
3 [1]
1 [nil]
27 [73]
57 [66]
26 [70]
40 [62]
28 [72]
39[65]
69 [26]
41 [31]
70 [28]
56 [36]
66 [25]
58[32]
1
2
3
Cyclohexene
Styrene oxide
Benzaldehyde
Phenyl acetaldehyde
Air
Argon
Air
Argon
Air
Argon
12
20
14
30
12
18
82
67
83
61
81
64
1
8
2
7
2
6
1
2
3
Styrene
a
Yields are represented with respect to the concentration of the oxidant.
Yields within braces after reduction with PPh3 prior to GC analysis.
b
ment of radicals rather than the participation of the metal-oxo
species.
tance of hydroxylated adamantane derivatives in pharmaceutical,
polymers and electronic industry. The catalytic reactions were
carried out in 3:2 acetonitrile/dichloromethane medium due to
the limited solubility of adamantane in pure acetonitrile. The
results are summarized in Table 2. The present catalytic sys-
tem oxidises adamantane mainly into 1-adamantanol along with
2-adamantanol as minor product. Here also, the perbrominated
manganese(III) corrole catalyst 3 emerges as the best among three
catalysts.
3.2. Catalytic oxidation of alkanes
At room temperature the catalytic activity of the manganese(III)
corroles (1–3) were examined for the alkane oxidations by tert-
butylhydroperoxide (t-BuOOH) in acetonitrile medium. Alkane
oxidation catalyzed by manganese(III) corrole has been achieved
for the first time. The results are summarized in Table 2. Cyclohex-
ane has been oxidized to cyclohexanol and cyclohexanone with A/K
values of 0.37–0.44. The highest overall conversion (22%) has been
achieved with the perbrominated manganese(III) corrole catalyst
3. The reduction of the reaction mixture by excess triphenylphos-
phine prior to GC analysis shows complete reversal of the product
pattern, i.e., cyclohexanol becomes the major product for all the
three catalysts (Table 2), which establishes the formation of cyclo-
hexyl hydroperoxide during the catalytic cycles.
To gain further insight into the mechanism of alkane oxida-
tion by the manganese(III) corroles/t-BuOOH system, adamantane
was chosen as a substrate, which is an important mechanistic
probe to diagnose the radical character of catalytic oxida-
tion reactions [44–47]. Furthermore, considerable efforts have
been devoted to introduce the hydroxyl group directly into
poorly reactive adamantane tricycles [48] due to the impor-
3.3. Catalytic oxidation of toluene
Oxidation of alkylbenzenes usually suffers from low selectivity
and mostly it is accompanied by the formation of various products
like benzaldehyde, benzyl alcohol, cresols, benzoic acid and diben-
zyl. Thus design of efficient process for the selective oxidation of
toluene is highly desirable. Under ambient condition the present
oxidizing system oxidises toluene to benzaldehyde as major prod-
uct, while benzyl alcohol is obtained as minor one. Reduction of
the reaction mixture with excess triphenylphosphine prior to the
GC analysis brings about a complete reversal in the product profile.
In this case, benzyl alcohol becomes the major product, support-
ing the involvement of benzyl peroxy radicals as one of the key
intermediates [49]. Among the manganese(III) corroles, catalyst 1
has been found to be most effective in bringing about oxidation of
Table 2
Catalytic oxidation of alkanes with t-BuOOH.
Substrate
Time (h)
Catalyst
Product profile (%)a,b
Cyclohexanol
Cyclohexanone
6
6
6
1
2
3
4 [9]
5 [12]
6 [14]
9 [5]
13 [6]
16 [8]
Cyclohexane
Adamantane-1-ol
Adamantane-2-ol
Adamantane
20
20
20
1
2
3
10
12
15
2
1
1
Benzaldehyde
Benzyl alcohol
Toluene
18
18
18
1
2
3
24 [7]
22 [8]
21 [8]
3 [19]
2 [16]
2 [14]
a
Yields are represented with respect to the concentration of the oxidant.
Yields within braces after reduction with PPh3 prior to GC analysis.
b

4
S. Bose et al. / Journal of Molecular Catalysis A: Chemical 332 (2010) 1–6
toluene and the relative activity of the catalysts follows the order
1 > 2 > 3.
3.4. Mechanistic consideration
The mechanism of manganese(III) corrole catalyzed alkene oxi-
dation by PhIO is not fully understood so far. Upon addition of PhIO
to the manganese(III) corroles, stable Mn(V)-oxo species forms
[31]. However, the oxomanganese(V) species is unreactive towards
alkenes and Gross et al. proposed that Mn(VI)-oxo species gen-
erated by disproportionation of Mn(V)-oxo complex is the active
oxidant. On the other hand, Goldberg et al. suggested that Mn(V)O
(PhIO) might be the true oxidant in the [Mn(III)(tpfc)]-catalyzed
oxidation of alkenes with PhIO [50]. Collman et al. had performed
competitive epoxidation of styrene and cyclooctene with differ-
ent iodosylarenes and argued in favour of multiple oxidants (both
Mn(V)O and Mn(III)-OIAr species) in [Mn(III)(tpfc)]-catalyzed oxi-
dation reactions [51]. With this background attempt has been
made to investigate the nature of oxidizing species involved in
the manganese(III) corrole/t-BuOOH catalytic system. The UV–vis
absorption spectral profiles of catalysts 1–3 in acetonitrile are
shown in Fig. 1. On addition of t-BuOOH to the manganese(III) cor-
roles, the split soret band disappears and new bands are generated
at 410 nm and 350 nm as shown in Fig. 2. The spectral profiles do not
correspond to the formation of the Mn(V)O complex. On compari-
son of the product pattern obtained in hydrocarbons oxidation by
the present manganese(III)corrole/t-BuOOH system with those of
manganese(III) corrole/PhIO [31] systems, it may be concluded that
the present reaction route is different from those found involving
the Mn(V)-oxo intermediate.
Fig. 1. Uv–vis spectra of catalysts 1 (brown), 2 (black) and 3 (green) in acetonitrile
at 25
◦C. (For interpretation of the references to color in this figure legend, the
reader is referred to the web version of the article.)
1
MnIII(corrole) + t-BuOOH
MnIV(corrole)(OH) + t-BuOOH
MnIV(corrole)(OOBu-t)
MnIV(corrole)(OH) + t-BuO•
MnIV(corrole)(OOBu-t) + H2O
MnIII(corrole) + t-BuOO•
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(11)
2 t-BuOO•
t-BuO• + RH
R• + O2
2 t-BuO• + O2
R• + t-BuOH
ROO•
ROH + R´=O + O2
R′=O + t-BuOH + O2
ROOH + R•
RO• + ROO• + H2O
ROH + R•
2 ROO•
ROO• + t-BuOO•
ROO• + RH
2ROOH
The involvement of radicals in the present oxidizing system
is evident from the fact that the oxidation of cyclohexene is
quenched completely in the presence of ‘radical scavenger’ 2,4,6-
tri-tert-butyl phenol. Also, in case of oxidation of adamantane, the
tertiary carbon atoms are preferentially activated over the sec-
ondary ones pointing towards the involvement of radicals. The
plausible reaction mechanism supporting all these results obtained
in the present case has been shown in Scheme 2. It seems rea-
sonable that the manganese(III) corroles (1–3) with t-BuOOH form
hydroxo-Mn(IV) species along with tert-butoxyl radical (step1). The
RO• + RH
Scheme 2. Simplified pathway for the oxidation of hydrocarbons by t-BuOOH in the
presence of manganese(III) corroles.
hydroxo-Mn(IV) species can further react with t-BuOOH, forming
MnIV-corrole (OOBu-t), which yields the tert-butylperoxy radicals
(step 3). The tert-butylperoxy radicals dismutate to tert-butoxyl
radical and dioxygen (step 4) [52–55]. The tert-butoxyl radical
Fig. 2. Overlay spectra of the catalyst 2 (25 ␮M) and TBHP (2 mM) in acetonitrile at 25 1 ◦C (successive spectrum taken after 3 min intervals). Inset: electronic spectrum of
(oxo)Mn(V) species generated in situ by the reaction of [Mn(III)(tpfc)] and PhIO.

S. Bose et al. / Journal of Molecular Catalysis A: Chemical 332 (2010) 1–6
5
Table 3
Values of (dA/dt)0 at ꢀ = 470 nm for the oxidation of [Mn(III)(tpfc)] by t-BuOOH in
acetonitrile at 25
30
y = 0.2279x + 3.1431
R2 = 0.9604
1
◦C.
25
20
15
10
5
Entry
[t-BuOOH]/
[Mn(III)(tpfc)]/
10−6 mol dm−3
(dA/dt)0/10−5 s−1
10−3 mol dm−3
1
2
3
4
5
6
7
8
1.04
1.92
2.88
3.84
1.92
1.92
1.92
1.92
35
35
35
35
18
30
50
76
6.407
10.382
13.924
17.463
6.019
10.926
15.601
19.682
0
abstracts an H-atom from the hydrocarbon with the formation of
alkyl or benzyl radicals (step 5). The process proceeds to the for-
mation of organo-peroxy radical (step 6), which either undergoes
a Russel-type termination [56] to form alcohols and ketones (in
case of cyclohexane and cyclohexene) (step 7) or decompose to
form aldehydes (in case of styrene and toluene). Alternatively, the
organo-peroxy radical can effect the homolytic cleavage of the C–H
bond of the hydrocarbon forming organo-hydroperoxide (step 9)
[43,57]. This species can then undergo homolytic decomposition to
the organooxyl RO• radical (step 10) followed by its H-abstraction
from the hydrocarbonformingthealcohol ROHandR• (step 11). The
involvement of the organo-hydroperoxide (ROOH) in the present
catalytic system is established by the significant increase in the
amount of alcohol with simultaneous decrease in the amount of
ketone (in case of cyclohexene, cyclohexane and toluene) when
the reaction mixture is treated with excess PPh3 prior to the GC
analysis using the well known method developed by Shul’pin et al.
[11,43,58,59].
10
20
30
40
50
60
70
80
[Mn(III)(tpfc)]/10-6mol dm-3
Fig. 4. Plots of (dA/dt)0 against [Mn(III)(tpfc)] at fixed [t-BuOOH] in acetonitrile at
25
◦C.
1
ear in [t-BuOOH] as well as in [Mn(III)(tpfc)]. The first order rate
constants obtained from Figs. 3 and 4 are 0.0392 s−1 and 2.279 s−1
respectively. The overall the reaction can be expressed as
dA
dt
−
= kd[t-BuOOH] [Mn(III)(tpfc)]
where kd is the second order rate constant. The value of
kd from the slope of the (dA/dt)0 vs. [t-BuOOH] at constant
[Mn(III)(tpfc)] is 1.1197 × 103 dm3 mol−1 s−1 while from the slope
of the (dA/dt)0 vs. [Mn(III)(tpfc)] at constant [t-BuOOH] a value of
kd of 1.187 × 103 dm3 mol−1 s−1 was obtained. The values obtained
for kd from the two different plots are thus in good agreement. The
rate constants of the elementary steps are relevant to the overall
catalytic process.
3.5. Kinetic studies
The transformation of manganese(III)-corrole to manganese(IV)
intermediate proceeds slowly, which is evident from Fig. 2. The rate
constants for the above transformation by t-BuOOH were measured
in acetonitrile. The change of absorbance at 470 nm was monitored
with time. It is observed that the absorbance vs. time plot does not
fit to a simple first or second order kinetic pattern. So the kinetic
data have been analyzed using the initial rate method [60–62]. Val-
ues of the initial rate (dA/dt0) for the reactions are compiled in
Table 3.
The values of (dA/dt)0 are plotted against [t-BuOOH] at constant
[Mn(III)(tpfc)] as shown in Fig. 3. Again, the plot of (dA/dt)0 vs.
[Mn(III)(tpfc)] at fixed [t-BuOOH] is displayed in Fig. 4. It is clear
from both the plots that the rate (dA/dt)0 for the reaction is lin-
4. Conclusion
At room temperature the oxygenation of alkenes, alkanes and
alkyl benzene has been achieved by the present oxidation system
comprising electron deficient manganese(III) corroles (1–3) as cat-
alysts and mild tert-butylhydroperoxide as terminal oxidant. The
use of tert-butylhydroperoxide as an oxidant in manganese(III) cor-
role calayzed oxidation reactions has been reported for the first
time. This is also the first description of using manganese(III) cor-
role for catalyzing oxidation of unactivated C–H bonds of alkanes.
It shows that the main role of the catalyst is the activation of
alkylhydroperoxide rather than oxygen atom transfer catalysis. The
achieved selectivity parameters are close to previously reported
oxidizing systems [37,43–45] that proceed with the participation
of alkylperoxy (ROO•) radicals and organo-hydroperoxide (ROOH).
During oxidation by the present oxidizing system, the involvement
of the organo-hydroperoxide (ROOH) has been confirmed. In con-
trast with the catalytic behaviour of manganese(III) corrole towards
peroxynitrite and hydrogen peroxide where the catalytic cycles
involve disproportionation with two-electron steps, the present
catalytic system proceeds through a radical-chain mechanism in
which the radicals are generated by oxidation and reduction of alkyl
hydroperoxide.
25
20
15
10
5
y = 3.9179x + 2.5627
R2 = 0.9975
0
Acknowledgements
0
1
2
3
4
5
[t -BuOOH]/10-3 mol dm-3
The financial support (SR/S1/IC-08/2007) from DST, Govern-
ment of India, is gratefully acknowledged. We thank UGC (India)
for the award of fellowships to AP & SB.
Fig. 3. Plots of (dA/dt)0 against [t-BuOOH] at fixed [Mn(III)(tpfc)] in acetonitrile at
25
◦C.
1

6
S. Bose et al. / Journal of Molecular Catalysis A: Chemical 332 (2010) 1–6
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