Alkane oxidation by the system 'tert-butyl hydroperoxide-[Mn 2L2O3][PF6]2 (L = 1,4,7trimethyl-1,4,7-triazacyclononane)-carboxylic acid'

Article abstract of DOI:10.1002/poc.1295

The kinetics of cyclohexane (CyH) oxygenation with terf-butyl hydroperoxide (TBHP) in acetonitrile at 50°C catalysed by a dinuclear manganese(IV) complex 1 containing 1,4,7-trimethyl-1,4,7-triazacyclononane and co-catalysed by oxalic acid have been studied. It has been shown that an active form of the catalyst (mixed-valent dimeric species 'Mn^IIIMn^IV,) is generated only in the interaction between complex 1 and TBHP and oxalic acid in the presence of water. The formation of this active form is assumed to be due to the hydrolysis of the Mn - O - Mn bonds in starting compound 1 and reduction of one Mn^IV to Mn^III. A species which induces the CyH oxidation is radical tert-BuO generated by the decomposition of a monoperoxo derivative of the active form. The constants of the equilibrium formation and the decomposition of the intermediate adduct between TBHP and 1 have been measured: k = 7.4mol^-1dm³ and k = 8.4 × 10 ^-2s^-1, respectively, at [H₂O] = 1.5 mol dm ^-3 and [oxalic acid] = 10^-2 mol dm^-3. The constant ratio for reactions of the monomolecular decomposition of tert-butoxy radical (tert-BuO → CH₃COCH₃+ CH₃) and its interaction with the CyH (terf-BuO + CyH → fert-BuOH + Cy) was calculated: 0.26 mol dm^-3. One of the reasons why oxalic acid accelerates the oxidation is due to the formation of an adduct between oxalic acid and 1 (K ≈ 10³ mol^-1 dm³). Copyright

Full text of DOI:10.1002/poc.1295

Research Article
Received: 2 September 2007,
Revised: 11 October 2007,
Accepted: 17 October 2007,
Published online in Wiley InterScience: 30 November 2007
(www.interscience.wiley.com) DOI 10.1002/poc.1295
Alkane oxidation by the system ‘tert-butyl
hydroperoxide–[Mn L O ][PF ] (L ¼ 1,4,7-
2
2 3
6 2
trimethyl-1,4,7-triazacyclononane)–
carboxylic acid’
a
a
a
Yuriy N. Kozlov , Galina V. Nizova and Georgiy B. Shul’pin *
The kinetics of cyclohexane (CyH) oxygenation with tert-butyl hydroperoxide (TBHP) in acetonitrile at 50 -C catalysed
by a dinuclear manganese(IV) complex 1 containing 1,4,7-trimethyl-1,4,7-triazacyclononane and co-catalysed by
oxalic acid have been studied. It has been shown that an active form of the catalyst (mixed-valent dimeric species
III
IV
‘
Mn Mn ’) is generated only in the interaction between complex 1 and TBHP and oxalic acid in the presence of water.
The formation of this active form is assumed to be due to the hydrolysis of the Mn—O—Mn bonds in starting
IV
III
.
compound 1 and reduction of one Mn to Mn . A species which induces the CyH oxidation is radical tert-BuO
generated by the decomposition of a monoperoxo derivative of the active form. The constants of the equilibrium
formation and the decomposition of the intermediate adduct between TBHP and 1 have been measured:
ꢀ
1
3
ꢀ2 ꢀ1
ꢀ3
ꢀ2
ꢀ3
K ¼ 7.4 mol dm and k ¼ 8.4 ꢁ 10
s
, respectively, at [H O] ¼ 1.5 mol dm and [oxalic acid] ¼ 10 mol dm
.
2
.
The constant ratio for reactions of the monomolecular decomposition of tert-butoxy radical (tert-BuO !
:
.
.
ꢀ3
CH
3
COCH
3
þ CH ) and its interaction with the CyH (tert-BuO þ CyH ! tert-BuOH þ Cy ) was calculated: 0.26 mol dm
.
3
One of the reasons why oxalic acid accelerates the oxidation is due to the formation of an adduct between oxalic acid
3
ꢀ1
3
and 1 (K ꢂ 10 mol dm ). Copyright ß 2007 John Wiley & Sons, Ltd.
Keywords: alkanes; alcohols; alkyl hydroperoxides; cyclohexane; cyclohexanol; homogeneous catalysis; kinetics; manganese
complexes; oxidation; tert-butyl hydroperoxide (TBHP)
in more detail the kinetics of the cyclohexane (CyH) oxidation by
TBHP catalysed with 1 in acetonitrile.
INTRODUCTION
tert-Butyl hydroperoxide (TBHP) is known as an efficient oxidizing
agent for the oxygenation of alkanes and other C—H
To demonstrate the formation of cyclohexyl hydroperoxide
(CyOOH) in CyH oxidations and to estimate its concentration in the
[
1]
compounds
to alkyl hydroperoxides, ketones (aldehydes)
course of the reaction we used a simple method developed by us
[2]
[14a,b,15]
and alcohols in reactions catalysed by complexes of ruthenium,
cobalt, copper, iron, rhodium, titanium and zirconium,
cerium, cromium, vanadium
earlier.
If an excess of solid PPh is added to the sample of
3
[3]
[4]
[5]
[6]
[7]
the reaction solution ca 10min prior the GC analysis, the alkyl
hydroperoxide present is completely reduced to the corresponding
alcohol. As a result, the chromatogram differs from that of a sample
not subjected to the reduction: the alcohol peak rises, while the
intensity of the ketone peak decreases. Comparing the intensities of
peaks attributed to the alcohol and ketone before and after the
reduction, it is possible to estimate the real concentrations of
alcohol, ketone and alkyl hydroperoxide present in the reaction
solution. In recent years, our method was applied by other chemists
[8]
[9]
[10]
[11]
and osmium.
Manganese
derivatives containing in many cases chelating N-ligands are
[12a–o]
among the most active catalysts in such oxidations.
It is
interesting that rhenium complexes are less efficient in oxi-
[12p–s]
dations of various C—H bonds.
that the dinuclear manganese(IV) complex [LMn(O)
complex 1; L is 1,4,7-trimethyl-1,4,7-triazacyclononane, TMTACN)
Earlier we discovered
3
MnL](PF
6 2
)
(
in the presence of a carboxylic acid efficiently catalyses oxi-
dations of alkanes and other organic compounds by hydrogen
[16]
in various oxidations of C—H compounds.
[
13]
[14]
peroxide (refer also to reviews ). Preliminary results showed
[13d,e]
that TBHP can be also used in such reactions.
In the present
RESULTS AND DISCUSSION
work, to get the information on a possible mechanism we studied
In preliminary works, we have found that the alkane oxidation
with TBHP in acetonitrile solution catalysed by complex 1 is
*
Semenov Institute of Chemical Physics, Russian Academy of Sciences, ulitsa
Kosygina, dom 4, Moscow 119991, Russia.
E-mails: gbsh@mail.ru; shulpin@chph.ras.ru
a
Y. N. Kozlov, G. V. Nizova, G. B. Shul’pin
This figure is available in colour online at www.interscience.wiley.com/
journal/poc
Semenov Institute of Chemical Physics, Russian Academy of Sciences, ulitsa
Kosygina, dom 4, Moscow 119991, Russia
J. Phys. Org. Chem. 2008, 21 119–126
Copyright ß 2007 John Wiley & Sons, Ltd.

Y. N. KOZLOV, G. V. NIZOVA AND G. B. SHUL’PIN
significantly accelerated if acetic acid is added into the reaction
In the present study, we decided to investigate first
[13d,e]
mixture.
of all the effect of various carboxylic acid in this reaction. In the
initial period, the reaction gives predominantly cyclohexyl
hydroperoxide (for the method of its determination, see above).
In our kinetic studies we were interested only in the maximum
reaction rates which were measured from sum of concentrations
of the products. To measure these concentrations we typically
3
reduced the samples of the reaction solutions with PPh and
determined the amounts of cyclohexanol and cyclohexanone.
This reduction leads to the most precise kinetic determinations.
We have found that logarithms of maximum reaction rates
a
linearly depend on the pK parameters for certain carboxylic
acids (Fig. 1). It can be seen that oxalic acid is more efficient as
a co-catalyst in comparison with acetic acid. Although this
difference is about only four times, we used oxalic acid in all our
further experiments.
Typical kinetic curves of the accumulation of the CyH
oxygenation products are shown in Fig. 2. The reaction rate is
significantly higher if oxalic acid is present in the solution
Figure 2. Kinetic curves of cyclohexanone þ cyclohexanol accumulation
ꢀ5
ꢀ3
)
(
compare curves 1 and 2). Kinetic curves correspond to the
current concentration cyclohexanone þ cyclohexanol after the
reduction of the reaction sample with PPh . The reaction begins
in the cyclohexane oxidation catalysed by complex 1 (5 ꢁ 10 mol dm
ꢀ2
in the absence (curve 1) and in the presence of oxalic acid (10 mol
ꢀ
3
¼ 0.46 mol dmꢀ3; [TBHP]
¼ 0.10 mol
dm ; curve 2). Conditions: [CyH]
0
0
3
ꢀ3
slowly, and only after 1.5 h the rate attains its maximum value. In
our further experiments, we measured this maximum rate. After
dm ; 50 8C.
3
h the rate gradually decreases.
We determined the current concentration of TBHP in the
that the lag period disappears (Fig. 3). In the case of other
carboxylic acids shortening of the lag period can be noticed only
after pre-treatment of all components without CyH and after
subsequent addition of CyH. These kinetic data testify that during
the initial slow period of the reaction a modification of the
course of the reaction and found that for the cases of all carbo-
xylic acids [TBHP] decreases not more than for 10–15% (when the
rate attains the maximum value), that is, it practically remains to
be equal to the initial concentration of TBHP. The CyH oxidation
occurs also in the absence of any carboxylic acid (curve 1, Fig. 2),
however, in this case the initial slow period of the reaction is
much longer. In the oxidation co-catalysed by oxalic acid the
initial slow lag period of the reaction can be shorten or even
removed completely if we use the reaction solution containing all
the components except either TBHP or CyH and pre-treated prior
the reaction at 50 8C for 1 h. If we introduce after such the
pre-treatment either TBHP or CyH, respectively, we can notice
Figure 3. Kinetic curves of cyclohexanone þ cyclohexanol accumulation
ꢀ
5
ꢀ3
)
in the cyclohexane oxidation catalysed by complex 1 (5 ꢁ 10 mol dm
ꢀ2
ꢀ3
Figure 1. Dependence of ln Wmax (where Wmax is the maximum reaction
rate attained in the beginning of the reaction) in the cyclohexane
and oxalic acid (10 mol dm ). Curve 1: all components were intro-
duced in the initial moment (time ¼ 0); curve 2: the reaction solution was
pre-treated at 50 8C for 1 h in the absence of TBHP and after that TBHP was
added at time ¼ 0; curve 3: the reaction solution was pre-treated at 50 8C
for 1 h in the absence of CyH and after that cyclohexane was added at
ꢀ
ꢀ3
5
ꢀ3
oxidation catalysed by complex 1 (5 ꢁ 10 mol dm ) in the presence
ꢀ4
of certain carboxylic acids (5 ꢁ 10 mol dm ) on the pK
a
parameters of
these acids: oxalic (1), malonic (2), succinic (3), glutaric (4), adipic (5)
¼ 0.46 mol dmꢀ ; [TBHP]
3
¼
time ¼ 0. Conditions: [CyH]
50 8C.
¼ 0.46 mol dmꢀ3; [TBHP]
¼ 0.10 mol dmꢀ3
;
and acetic (6) acids. Conditions: [CyH]
0
0
0
0
ꢀ
3
0
.1 mol dm ; 50 8C.
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Copyright ß 2007 John Wiley & Sons, Ltd.
J. Phys. Org. Chem. 2008, 21 119–126

ALKANE OXIDATION
III
IV
catalyst precursor 1 occurs, and complex 1 is transformed into a
new species which is more catalytically active one.
conversion 1 ! ‘Mn Mn ’ is accelerated by adding a carboxylic
acid. As the rate of this transformation depends on the nature of
the carboxylic acid and its concentration one can assume that the
conversion of 1 includes the primary stage of the hydrolysis of the
Our studies using UV–Vis spectroscopy support the conclusion
about the formation of a more active in catalysis species. Figure 4
demonstrates the spectra of the reaction solution at time ¼ 0
IV
oxo bond in compound 1. Then the reduction of one Mn ion to
produce the Mn ion occurs followed by some changes in the
species structure which is a dimer as previously. The existence of
III
(curve 1) and at the moments when the reaction rate is
sufficiently increased approaching to its maximum value (curve 2)
and when the reaction deceases (curve 3). It can be seen that the
curves differ dramatically. According to the data by Wieghardt
III
IV
the dimeric structure of the ‘Mn Mn ’ species is supported by a
similarity of the absorption spectra obtained for our system and
previously published for synthesized dimeric complexes contain-
[17]
et al. the absorption in the region 500 nm in the spectrum 2 is
due to the dimeric structure of a mixed-valent complex
[
17]
ing manganese ions.
It should be noted that in our further studies, the maximum
III
IV
‘
Mn Mn ’. This species can contain two m-oxo bridges and also
[17]
oxalate as the third bridge. An increase of the oxygenation rate
rate, Wmax, of the cyclohexanone þ cyclohexanol accumulation
III
IV
occurs simultaneously with the increase of the species ‘Mn Mn ’
concentration. The subsequent decrease of the rate correlates
with the disappearance of this species. Based on this observation
we can assume that the complex ‘Mn Mn ’ is the most active in
the oxygenation species.
(after reduction with PPh ) was used as a kinetic parameter of the
3
system. The maximum rate is attained after practically complete
transformation of the oxo complex 1 into the mixed-valent
‘Mn Mn ’ species. This parameter was considered as the initial
stationary reaction rate (because TBHP consumption is negli-
gible). Such a rate corresponds to the catalysis by the
mixed-valent ‘Mn Mn ’ species which concentration is equal
to the concentration of 1. We should also emphasize that only
oxalic acid has reducing properties unlike all other carboxylic
acids studied here. Nevertheless, reducing ability of oxalic acid
does not play any sufficient role in the process of active species
generation because the formation rate of this species is much
higher in the presence of TBHP (since TBHP can also play the role
of a reducing agent). Figure 1 demonstrates the stationary
reaction rates, that is, the rates when the transformation of all
amount of the initial complex into the active species is comp-
leted. We can assume that the correlation between the rate and
the pK-value corresponds to the effect of the carboxylic acid on
III
IV
III
IV
An important feature of oxalic acid as a co-catalyst was the fact
that only in its presence we can observe a slow (more slow than it
was under the conditions of the catalytic alkane oxidation)
III
IV
III
IV
conversion of complex 1 to a ‘Mn Mn ’ species even in the
absence of TBHP. This fact can be due to the reducing properties
of oxalic acid in contrast to the properties of other acids studied in
this work. It is reasonable to assume that it is the TBHP which
plays the role of a reducing agent in the catalytic process in the
presence of other acids.
Our experimental data suggest that the transformation of
III
IV
complex 1 into the ‘Mn Mn ’species occurs with participation of
water molecules (in the anhydrous acetonitrile solution complex
1
is stable and its optical spectrum is not changed with time). The
III
IV
the catalytic activity of the ‘Mn Mn ’ species. This effect is the
result of a coordination of the acid to manganese ions and is by
no means due to the reducing properties of this particular acid.
We have found that the products of the CyH oxidation are
formed with participation of molecular oxygen. Indeed, when the
reaction was carried out under argon atmosphere the yield of
oxygenates became lower more than for 70%. The effect of O on
2
the yield of the products allows us to assume a radical
mechanism for the CyH oxidation.
Table 1 summarizes selectivity parameters for the oxidation of
various alkanes by the ‘1/TBHP/oxalic acid’ system as well as (for
comparison) by some other oxidizing systems. It can be seen that
the selectivity parameters for the oxidations with ‘1/TBHP/oxalic
acid’ system (e.g. entry 1) are noticeably different from the
parameters found previously for systems generating hydroxyl
radicals (entries 5 and 6). However, these parameters are close to
that measured for the oxidations by other systems oxidizing with
participation of tert-butoxy radicals (entry 7). This observation
allows us to propose that alkane-oxidizing species which is
.
generated by the system under discussion is radical tert-BuO .
We have obtained also a kinetic evidence which supports this
hypothesis. Let us analyse the mode of dependence of the
maximum CyH oxidation rate on the CyH concentration shown in
Fig. 5. As CyH does not form any adducts with the catalyst it is
reasonable to assume that the mode of the dependence under
discussion testifies the generation in the system of an oxidizing
Figure 4. UV–Vis spectra of the reaction solution in the cyclohexane
ꢀ5
ꢀ3
oxidation catalysed by complex 1 (5 ꢁ 10 mol dm ) and oxalic
ꢀ
2
ꢀ3
ꢀ3
,
species. According to the selectivity parameters this species is
acid (10 mol dm ). Other conditions: [TBHP]
0
¼ 0.10 mol dm
.
ꢀ3
tert-BuO . The rate of this generation is W
:
1
[
cyclohexane]
0
¼ 0.46 mol dm , solvent was acetonitrile, 50 8C. Spectra
were recorded at 0 (1), 30 (2) and 70 (3) min after mixing the reactants.
This figure is available in colour online at www.interscience.wiley.com/
journal/poc
cat
TBHP ꢀ! tertꢀBuOꢃ
(1)
J. Phys. Org. Chem. 2008, 21 119–126
Copyright ß 2007 John Wiley & Sons, Ltd.
www.interscience.wiley.com/journal/poc

Y. N. KOZLOV, G. V. NIZOVA AND G. B. SHUL’PIN
a
Table 1. Selectivity parameters for the alkane oxidations by various systems
Entry
Alkane
Oxidizing system
Selectivity
n-Octane
C(1):C(2):C(3):C(4)
1
2
3
4
5
6
7
TBHP–1–oxalic acid in MeCN; 50 8C
1.0:17.3:12.0:10.5
1:50:47:40
1:19:21
1.0:29:25:24
1.0:10.2:6.8:6.3
1.0:9.3:8.8:7.2
1:14:9:13
18:28:38
1.0:1.6:43
1:32:336
1:19:204
1.0:6.0:34
1.0:5.5:18
1.0:5.5:24
18:28:38
1.0:0.4:32
1.0:0.6:100
1:16:202
1.0:4.0:20
1.0:2.0:32
1.0:3.0:12
1:0:41
TBHP–1–oxalic acid in H
TBHP–1–oxalic acid in H
2
O; 50 8C
O; 50 8C
b
2
c
H O –1–acetic acid in MeCN; 20 8C
2
2
2
2
2
2
d
H
O
–hn in MeCN; 20 8C
–Bu NVO –PCA in MeCN; 30 8C
d
e
H
O
4
3
TBHP–Cu(MeCN) BF in MeCN; 60 8C
4
4
2
-Methylhexane
8
9
0
0
1
2
TBHP–1–oxalic acid in MeCN; 50 8C
TBHP–1–oxalic acid in H O; 50 8C
2
f
1
1
1
1
H O –1–acetic acid in MeCN; 20 8C
2
2
d
H
2
O
2
–hn in MeCN; 20 8C
TBHP–hn in MeCN; 20 8C
d
H O –Bu NVO –PCA in MeCN; 30 8C
2
2
4
3
Isooctane
1
1
1
1
1
1
1
3
4
5
6
7
8
9
TBHP–1–oxalic acid in MeCN; 50 8C
TBHP–1–oxalic acid in H O; 50 8C
2
H
H
2
O
2
–1–acetic acid in MeCN; 20 8C
–hn in MeCN; 20 8C
d
2
O
2
TBHP–hn in MeCN; 20 8C
–Bu NVO –PCA in MeCN; 30 8C
TBHP–Cu(MeCN) BF
d
e
H
2
O
2
4
3
4
4
in MeCN; 60 8C
Methylcyclohexane
18:28:38
1.0:0.3:0.6
1.0:2.0:6.0
1.0:3.0:5.0
trans/cis
0.2
20
21
22
TBHP–1–oxalic acid in MeCN; 50 8C
d
H
H
2
O
2
–hn in MeCN; 20 8C
–Bu NVO –PCA in MeCN; 30 8C
d
2
O
2
4
3
cis-1,2-Dimethylcyclohexane
2
2
2
2
2
2
3
4
6
5
6
7
TBHP–1–oxalic acid in MeCN; 50 8C
TBHP–1–oxalic acid in H O; 50 8C
2
0.6
0.34
0.9
c
H O –1–acetic acid in MeCN; 20 8C
2
2
d
H
2
O
2
–hn in MeCN; 20 8C
TBHP–hn in MeCN; 20 8C
H O –Bu NVO –PCA in MeCN; 30 8C
1.0
0.75
trans/cis
7.3
4.1
1.0
0.8
trans/cis
0.45
0.12
d
d
d
2
2
4
3
trans-1,2-Dimethylcyclohexane
28
29
30
31
TBHP–1–oxalic acid in MeCN; 50 8C
c
H
2
O
2
–1–acetic acid in MeCN; 20 8C
d
H O –hn in MeCN; 20 8C
2
2
H
2
O
2
–Bu
4
NVO
3
–PCA in MeCN; 30 8C
cis-Decalin
32
33
34
35
TBHP–1–oxalic acid in MeCN; 50 8C
c
H
H
2
O
2
–1–acetic acid in MeCN; 20 8C
–hn in MeCN; 20 8C
d
2
O
2
1.3
2.1
H O –Bu NVO –PCA in MeCN; 30 8C
2
2
4
3
a
All parameters were measured after reduction of the reaction mixtures with triphenylphosphine before GC analysis and calculated
based on the ratios of isomeric alcohols. Parameters C(1): C(2): C(3): C(4) are relative and normalized (i.e. calculated taking into
account the number of hydrogen atoms at each carbon) reactivities of hydrogen atoms at carbons 1, 2, 3 and 4, of the chain of linear
alkanes. Parameters 18: 28: 38 are relative and normalized reactivities of hydrogen atoms at primary, secondary and tertiary carbons of
branched alkanes. Parameter trans/cis is the ratio of trans- and cis-isomers of tert-alcohols formed in the oxidation of 1,2-disubstituted
cyclohexanes (cis-DMCH, trans-DMCH and cis-decalin).
b
n-Hexane was used instead of n-octane.
For this system, refer to Reference [13a-d].
These systems are believed to operate via generating hydroxyl radicals. Refer to References [14a,b,15d,f,18] n-Heptane was used
c
d
[14a,b,15d,f,18]
instead of n-octane. In the ‘H
2
O
2
–vanadate–PCA’ reagent
PCA is pyrazine-2-carboxylic acid.
e
For this system, refer to Reference [4].
-Methylpentane was used instead of 2-methylhexane. Refer to Reference [13c].
f
2
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Copyright ß 2007 John Wiley & Sons, Ltd.
J. Phys. Org. Chem. 2008, 21 119–126

ALKANE OXIDATION
Figure 6. A linear anamorphosis of dependence ꢀd[CyH]/dt ¼ f([CyH]
0
)
Figure 5. Dependence of the maximum rate of the cyclohexano-
ne þ cyclohexanol accumulation in the cyclohexane oxidation catalysed
presented in Fig. 5. This figure is available in colour online at www.
interscience.wiley.com/journal/poc
ꢀ5
ꢀ3
ꢀ2
ꢀ3
by complex 1 (5 ꢁ 10 mol dm ) and oxalic acid (10 mol dm
)
on initial concentration of cyclohexane. Conditions: [TBHP]
0
¼
ꢀ3
0.10 mol dm ; acetonitrile; 50 8C. This figure is available in colour online
The maximum CyH oxidation rate is in direct ratio to
concentration of catalyst 1 (Fig. 7). Dependence of Wmax on
initial concentration of TBHP at constant water concentration
at www.interscience.wiley.com/journal/poc
ꢀ
3
Here cat is a catalytically active species derived from complex
([H
2
O] ¼ 1.5 mol dm ) is presented in Fig. 8. The mode of this
1
. The oxidizing species disappears in two parallel reactions. One
shape allows us to assume that an intermediate adduct between
TBHP and cat is formed. Using a simple kinetic model for the
generation of active species shown below:
.
of these processes is the interaction between tert-BuO and CyH:
ꢃ
ꢃ
tertꢀBuO þ CyH ! tertꢀBuOH þ Cy
(2)
k5
[19]
ꢅ
In accordance with the literature we may also consider the
cat þ tert-BuOOH @ cat tert-BuOOH
(5)
kꢀ5
monomolecular decay of tert-butoxy radical:
k6
CyH
ꢅ
ꢃ
ꢃ
ꢃ
cat tert-BuOOH ꢀ! tert-BuO ꢀ! . . .
and analysing this scheme in a quasi-equilibrium approximation
we will obtain the following equation:
(6)
tertꢀBuO ! CH3COCH3 þ CH
(3)
3
As in the presence of molecular oxygen both cyclohexyl and
methyl radicals are rapidly transformed into peroxy radicals
which exhibit low reactivity we can say that reactions (2) and (3)
are the processes of consumption of active species. Detectable
products of the CyH oxidation are formed as a result of the total
rate-non-limiting subsequent stages of the cyclohexyl radical
transformations.
d½CyHꢄ dS½productsꢄ
K5½TBHPꢄ½catꢄ
1 þ K5½TBHPꢄ
i
ꢀ
¼
¼ 0:64k6
(7)
dt
dt
The analysis of the kinetic scheme (1)–(3) based on an
.
assumption that concentration of tert-BuO is quasi-stationary led
to the following equation for the CyH oxidation rate:
d½CyHꢄ
dt
W1
k3
k2½CyHꢄ
ꢀ
¼ 1
(4)
þ
The experimental data presented in Fig. 5 obey this equation
because a linear dependence of the reciprocal rate of CyH
oxidation on reciprocal CyH concentration is observed (Fig. 6). We
ꢀ
6
ꢀ3 ꢀ1
can calculate parameters W ¼ 1.7 ꢁ 10 mol dm
s and k3/
1
ꢀ
3
k
2
¼ 0.26 mol dm using values for the tangent of slope of the
line shown in Fig. 6 and the segment which this line cuts off on
the y-axis. The value of the constant ratio k /k agrees (with
3
2
ꢀ
3
reasonable accuracy) with the value 0.19 mol dm taken from
the literature. In Reference [19] parameter k /k was obtained
3 2
[19]
from the ratio of the yields of acetone and tert-butanol [refer to
reactions (2) and 3)] during the photochemical generation of
tert-BuO radicals in acetonitrile solution in the presence of CyH at
the temperature of our kinetic experiments. These results are an
additional support for our assumption that the tert-butoxy radical
is the oxidizing species which operates in the catalytic system
under discussion.
.
Figure 7. Dependence of the maximum rate of the cyclohexano-
ne þ cyclohexanol accumulation in the cyclohexane oxidation catalysed
ꢀ2
ꢀ3
by complex 1 and oxalic acid (10 mol dm ) on initial concentration of
ꢀ
3
ꢀ3
1
. Conditions: [TBHP]
0
¼ 0.10 mol dm ; [CyH]
0
¼ 0.46 mol dm ; aceto-
nitrile; 50 8C. This figure is available in colour online at www.interscience.
wiley.com/journal/poc
J. Phys. Org. Chem. 2008, 21 119–126
Copyright ß 2007 John Wiley & Sons, Ltd.
www.interscience.wiley.com/journal/poc

Y. N. KOZLOV, G. V. NIZOVA AND G. B. SHUL’PIN
the effective parameters because the reaction rate depends on
concentrations of both water and oxalic acid. The values given
ꢀ
3
above correspond to [H
¼
2
O] ¼ 1.5 mol dm and [oxalic acid] -
ꢀ2
ꢀ3
10 mol dm .
Our data show that the reaction rate depends not only on the
nature of the carboxylic acid (Fig. 1) but also on its concentration
Fig. 10). The mode of dependence of Wmax on concentration of
(
oxalic acid (Fig. 10) shows that an activation of the catalyst
precursor 1 is possible via the formation of an adduct between 1
and oxalic acid. However, we realize that based only on the results
of Fig. 10 a strict demonstration of the adduct formation is
problematic since we do not know the effect of the medium
acidity on the formation constant for this adduct and also on its
catalytic activity. Nevertheless, we can estimate the effective
equilibrium constant at fixed [TBHP] assuming that the formation
of an adduct between initial manganese compound and oxalic
acid leads to the activation of the catalyst. Let us denote all
dimeric species containing manganese ions as ‘Mn ’ including to
2
this formula intermediates which both contain and do not
contain TBHP but do not contain oxalic acid (the concentrations
of such species are controlled by the corresponding equilibrium
Figure 8. Dependence of the maximum rate of the cyclohexano-
ne þ cyclohexanol accumulation in the cyclohexane oxidation catalysed
by complex 1 and oxalic acid on initial concentration of TBHP. Condi-
ꢀ5
ꢀ3
ꢀ2
ꢀ3
tions: [1] ¼ 5 ꢁ 10 mol dm ; [oxalic acid] ¼ 10 mol dm ; [CyH]
0
¼
constants for the formation of peroxo complexes). In this case, we
ꢀ
3
ꢀ3
.
0
.46 mol dm ; [H
2
O] ¼ 1.5 mol dm ; acetonitrile; 50 8C. This figure is
can denote as ‘Mn
’ (COOH)
all adducts between dinuclear
2
2
available in colour online at www.interscience.wiley.com/journal/poc
manganese species and oxalic acid. We will come to equation:
K9
To simplify further analysis of the data from Fig. 8 let us
transform Eqn (7) into the following one:
0
Mn2 þ ðCOOHÞ @ Mn2 0ꢃðCOOHÞ
0
0
(9)
2
2
Constant of this equilibrium K is the effective parameter which
depends on concentrations of TBHP, water as well as on the
acidity of the reaction medium. In the half-effect point
9
ꢀ
ꢁꢀ
ꢀ
ꢁ
1
d½CyHꢄ
dt
1
1
ꢀ
¼
1 þ
(8)
0:64k6½catꢄ
K5½TBHPꢄ
.
[
‘Mn ’] ¼ [‘Mn ’ (COOH) ], that is, K [(COOH) ] ¼ 1 because oxalic
2
2
2
9
2
It follows from the data of Fig. 9 (which presents the linear
anamorphosis of the curve shown in Fig. 8) that the
experimentally obtained parameters with reasonable accuracy
correspond to the proposed model and are in the quantitative
acid is present in a great excess over catalyst precursor 1. It
ꢀ
3
follows from data of Fig. 10 that at [TBHP] ¼ 0.1 mol dm and
ꢀ3
[H O] ¼ 1.5 mol dm the half-effect is attained at [(COOH) ] ꢂ
2
ꢀ
2
3
ꢀ3
3
ꢀ1
3
10 mol dm and, consequently, K ꢂ 10 mol dm .
9
ꢀ1
3
agreement with this model if we assume K ¼ 7.4 mol dm and
5
2
ꢀ1
k
6
¼ 8.4 ꢁ 10ꢀ
s . It should be noted that values K
5 6
and k are
Figure 10. Dependence of the maximum rate of the cyclohexano-
ne þ cyclohexanol accumulation in the cyclohexane oxidation catalysed
by complex 1 and oxalic acid on concentration of oxalic acid. Condi-
ꢀ
5
ꢀ3
ꢀ3
Figure 9. A linear anamorphosis of dependence ꢀd[CyH]/dt ¼
f([TBHP] ) presented in Fig. 8. This figure is available in colour online
tions: [1] ¼ 5 ꢁ 10 mol dm
;
[CyH]
0
¼ 0.46 mol dm
;
[TBHP]
0
¼
ꢀ3
0
0.10 mol dm ; acetonitrile; 50 8C. This figure is available in colour online
at www.interscience.wiley.com/journal/poc
at www.interscience.wiley.com/journal/poc
www.interscience.wiley.com/journal/poc
Copyright ß 2007 John Wiley & Sons, Ltd.
J. Phys. Org. Chem. 2008, 21 119–126

ALKANE OXIDATION
of the catalysed TBHP decomposition is its molecular decay.
.
Another process – with generation of tert-BuO radicals – is only a
minor route. The rate ratio for these two routes of the catalytic
TBHP transformation is close to 10. It explains why the system
uses only ca 10% of TBHP for the CyH oxygenation whereas 90%
decomposes non-productively.
EXPERIMENTAL
[17]
Complex 1 was synthesized as described in Reference
. The
oxidations of hydrocarbons were carried out in acetonitrile in air
in thermostated (25 8C) Pyrex cylindrical vessels with vigorous
stirring. The total volume of the reaction solution was 2 ml.
Initially, a portion of TBHP (70% aqueous) was added to a solution
of the catalyst 1, co-catalyst (typically oxalic acid) and CyH. After
certain time intervals samples (about 0.2 ml) were taken. To
determine the concentration of a sum of the stable CyH oxidation
products (cyclohexanone and cyclohexanol) the sample of the
reaction solution was typically treated with PPh
3
(for this method,
[14a,b,15]
refer to References
) and analysed by GC (LKhM-80-6
Figure 11. Kinetic curves of TBHP consumption under the action of 1
and oxalic acid in the presence (curve 1) and in the absence (curve 2)
instrument, columns 2 m with 5% Carbowax 1500 on 0.25–
0.315 mm Inerton AW-HMDS; carrier gas was argon). Other
saturated hydrocarbons were oxidized under analogous con-
ditions. Concentration of TBHP was measured by titration of the
reaction mixture aliquots with 0.1 mol dm NaI in acetic an-
hydride (control by UV–Vis spectroscopy).
ꢀ
5
ꢀ3
of cyclohexane. Conditions: [1] ¼ 5 ꢁ 10 mol dm
;
[oxalic acid] -
ꢀ
2
ꢀ3
ꢀ3
ꢀ3
¼
10 mol dm
;
[CyH]
0
¼ 0.46 mol dm
;
[TBHP]
0
¼ 0.10 mol dm
;
50 8C.
ꢀ3
We have demonstrated that the rate of the TBHP decompo-
sition in the presence and in the absence of CyH is practically the
same (Fig. 11) and that this rate is a few times higher than the CyH
oxygenation rate (Fig. 12). As the CyH oxidation is induced by
tert-butoxy radicals (see above) the rate of its transformation into
Acknowledgements
This work was supported by the Russian Basic Research Founda-
tion (No. 06-03-32344-a).
oxygenates at [CyH] ! 1 is equal to the rate of generation of
.
tert-BuO radicals in the catalysed TBHP decomposition. Addition
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Conditions: [1] ¼ 5 ꢁ 10 mol dm
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J. Phys. Org. Chem. 2008, 21 119–126
Copyright ß 2007 John Wiley & Sons, Ltd.
www.interscience.wiley.com/journal/poc

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