Oxidation of alkanes and alcohols with hydrogen peroxide catalyzed by complex Os3(CO)10(μ-H)2

Article abstract of DOI:10.1002/aoc.1641

Trinuclear carbonyl hydride cluster, Os₃(CO)₁₀(μ- H)₂, catalyzes oxidation of cyclooctane to cyclooctyl hydroperoxide by hydrogen peroxide in acetonitrile solution. The hydroperoxide partly decomposes in the course of the reaction to afford cyclooctanone and cyclooctanol. Selectivity parameters obtained in oxidations of various linear and branched alkanes as well as kinetic features of the reaction indicated that the alkane oxidation occurs with the participation of hydroxyl radicals. A similarmechanism operates in transformation of benzene into phenol and styrene into benzaldehyde. The system also oxidizes 1-phenylethanol to acetophenone. The kinetic study led to a conclusion that oxidation of alcohols does not involve hydroxyl radicals as main oxidizing species and apparently proceeds with the participation of osmyl species, 'Os = O'. Copyright

Full text of DOI:10.1002/aoc.1641

Full Paper
Received: 16 December 2009
Revised: 5 February 2010
Accepted: 7 February 2010
Published online in Wiley Interscience: 24 March 2010
(www.interscience.com) DOI 10.1002/aoc.1641
Oxidation of alkanes and alcohols
with hydrogen peroxide catalyzed by complex
†
Os3(CO)10(µ-H)2
Georgiy B. Shul’pina∗, Yuriy N. Kozlova, Lidia S. Shul’pinab
and Pavel V. Petrovskiyb
Trinuclear carbonyl hydride cluster, Os3(CO)10(µ-H)2, catalyzes oxidation of cyclooctane to cyclooctyl hydroperoxide by
hydrogen peroxide in acetonitrile solution. The hydroperoxide partly decomposes in the course of the reaction to afford
cyclooctanone and cyclooctanol. Selectivity parameters obtained in oxidations of various linear and branched alkanes as well
as kinetic features of the reaction indicated that the alkane oxidation occurs with the participation of hydroxyl radicals. A
similar mechanism operates in transformation of benzene into phenol and styrene into benzaldehyde. The system also oxidizes
1-phenylethanol to acetophenone. The kinetic study led to a conclusion that oxidation of alcohols does not involve hydroxyl
c
radicals as main oxidizing species and apparently proceeds with the participation of osmyl species, ‘Os O’. Copyright ꢀ 2010
John Wiley & Sons, Ltd.
Supporting information may be found in the online version of this article.
Keywords: alkanes; alcohols; alkyl hydroperoxides; homogeneous catalysis; hydrogen peroxide; hydroperoxidation; ketones; osmium
complexes
Introduction
pronounced auto-acceleration, which indicates that compound
1 is a precatalyst of this reaction. Catalytically active species are
formed during first hour of the process and after that the reaction
proceeds with maximum rate. Maximum yield of products (34%)
based on cyclooctane was attained after 6.5 h (Fig. 1, graph A).
Maximum turnover number, that is number of moles of products
per 1 mol of the catalyst was attained (TON = 1400) after 5 h and
maximum turnover frequency (TOF = TON per 1 h) was reached
(480 h−1)between1and2 h(seeFig. 1B). Itcanbeseenthatkinetic
curves for conditions of experiments shown in Fig. 1(A and B) are
quite similar. However, at higher concentrations of 1 (5 × 10−4 M;
Fig. 1A) the final yields of all products are higher and the amounts
of cyclooctanone and cyclooctanol are also higher.
Complexes of various transition metals and particularly
organometallic derivatives are well-known catalysts for oxidations
of hydrocarbons[1,2] and alcohols[3] with peroxides, predominantly
hydrogen peroxide. Osmium derivatives have been reported to
efficiently catalyze oxidation of olefins with peroxides.[4] In con-
trast, relatively few publications have been devoted to osmium-
catalyzed oxidations of saturated and aromatic hydrocarbons and
alcohols.[5,6] Here, we have explored the possibility of complex
Os3(CO)10(µ-H)2 to catalyze oxidation of alkanes and alcohols with
hydrogen peroxide.
The nature of the alkane oxidizing species can be evaluated
if we measure the selectivity parameters in oxidations of certain
alkanes (Table 1, entry 1). It can be seen that these parameters are
close to the selectivities determined previously for the systems
generating hydroxyl radicals (entries 2–8) and noticeably lower
Results and Discussion
We have found that trinuclear carbonyl hydride cluster,
Os3(CO)10(µ-H)2 (compound 1, Scheme 1), catalyzes oxidation of
cyclooctane (2, Scheme 2) to cyclooctyl hydroperoxide (3), which
partly decomposes in the course of the reaction to afford cy-
clooctanone (4) and cyclooctanol (5) by hydrogen peroxide in
acetonitrile solution. The same system oxidizes 1-phenylethanol
(6) to acetophenone ( 7).
Accumulation of the oxygenates in the oxidation of cyclooctane
at two different initial concentrations of catalyst 1 and H2O2 is
shown in Fig. 1. It can bee seen that cyclooctyl hydroperoxide is
the main product which decomposes to produce cyclooctanone
and cyclooctanol. Concentrations of the three products were
measured by GC comparing concentrations of cyclooctanone and
cyclooctanol before and after reduction of the reaction mixture
withanexcessofPPh3.Forthismethoddevelopedpreviously;[1a,f,g]
see the Experimental. The formation of oxygenates occurs with
∗
Correspondence to: Georgiy B. Shul’pin, Semenov Institute of Chemical Physics,
KineticsandCatalysis,ul.Kosygina,dom4,Moscow119991,RussianFederation.
E-mail: gbsh@mail.ru
†
a
Part 2 of the series ‘Oxidations catalyzed by osmium compounds’. For part 1,
see Shul’pin et al.[5g]
.
Semenov Institute of Chemical Physics, Russian Academy of Sciences, ulitsa
Kosygina, dom 4, Moscow 119991, Russia
b
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of
Sciences, ulitsa Vavilova, dom 28, Moscow 119991, Russia
c
Appl. Organometal. Chem. 2010, 24, 464–472
Copyright ꢀ 2010 John Wiley & Sons, Ltd.

Oxidation of alkanes and alcohols with hydrogen peroxide
Oxidation of benzene (0.5 M) with H2O2 (2 M) in the presence
of 1 (5 × 10−4 M) during 1 h at 60 ◦C gave phenol (0.05 M, yield
10%) and oxidation of styrene under the same conditions afforded
benzaldehyde (0.06 M, yield 13%). These results testify that the
oxidation occurs with the participation of hydroxyl radicals.
Consumption of 1-phenylethanol in its oxidation and accumu-
lation of acetophenone are shown in Fig. 2. No auto-acceleration
can be noticed in this case unlike in the oxidation of cyclooctane.
When the hydrogen peroxide–alcohol ratio is 2.5, maximum yield
(60%) of acetophenone is attained after 10 h (Fig. 2B). If hydro-
gen peroxide is used in a larger excess (5 : 1) over-oxidation of
acetophenone takes place after 6 h (Fig. 2C).
A
0.16
3
0.12
0.08
0.04
4
0
5
0
2
4
6
8
We studied the dependences of the initial rate of the
transformation of 1-phenylethanol to acetophenone W0 on initial
concentrations of the reactants. Rate W0 linearly depends on
concentration of pre-catalyst 1 (Fig. 3). The dependence of W0 on
initial concentration of 1-phenylethanol is shown in Fig. 4(B). It
is noteworthy that initial rate increases if some amount of water
is added to the reaction solution (Fig. 5). Finally, W0 practically
does not depend on initial concentration of hydrogen peroxide
at [H2O2]0 > 1 M if total concentration of water is maintained
constant (9 M) (Fig. 6).
B
0.16
0.12
3
0.08
0.04
0
4
5
Let us discuss a possible mechanism of oxidation of alkanes and
alcohols. The catalytic system under consideration demonstrates
at the first glance contradictory properties. On the one hand,
low selectivity parameters of the alkane oxygenation (see Table 1)
allow us to assume that a species oxidizing alkanes is hydroxyl
radicals. On the other hand, it is doubtful that a high degree
of phenylethanol conversion to acetophenone (see Fig. 2B)
can be attained in the case of attack of hydroxyl radicals at
1-phenylethanol containing reactive phenyl substituent. Indeed,
theanalysisofdatagiveninFarhataziz[8] showsthattheprobability
of the interaction between radical HO· and the benzene ring is
higher than that between HO· and the alcohol group. Because
of this, one could expect the formation in this case of large
amounts of oxidative transformation of the benzene ring. In
contrast, the real yield of such products is not high. Thirdly, the
mode of the dependence of W0 for 1-phenylethanol oxidation
on its initial concentration (see Fig. 4A) is not in accordance
with the assumption that the alcohol oxidation occurs with the
participation of hydroxyl radicals. It is known that in the case of
oxidations with the participation of hydroxyl radicals (for example,
for the systems H2O2 –hν, H2O2 –vanadate–PCA in acetonitrile,
see Shul’pin et al.[2t,7a,d,e]), even when substrates react with HO·
with the rate constant lower that that for 1-phenylethanol, value
W0 practically does not depend on substrate concentration if
this concentration is higher than ca 0.5 M. It follows from the
data demonstrated in Fig. 4(A) that the rate of 1-phenylethanol
oxidation on catalyst 1 continues to grow even at [6]0 > 0.5 M,
despite the rate constant of the interaction between 6 and HO·
being approximately one order of magnitude higher than the
corresponding constant for cyclohexane.
0
2
4
6
8
Time / h
Figure 1. Accumulation (concentration, M) of cyclooctyl hydroperoxide
(3), cyclooctanone (4) and cyclooctanol (5) in the oxidation of cyclooctane
(2) with time. Concentrations of these products in the reaction solution
were measured by comparison of chromatograms prepared before and
after reduction of the samples with an excess of PPh3 (for this method,
see Shul’pin[1a,f,g] and Experimental). Conditions: [cyclooctane]0 = 0.5
M; 60 ◦C; solvent, acetonitrile; total volume of the reaction solution, 5 ml.
(A) [1]0 = 5×10−4 M,[H2O2]0 = 1.0M.(B) [1]0 = 1×10−4 M,[H2O2]0 = 1.5
M.
CO
Os
CO
OC
Os
OC
CO
OC
OC
CO
H
Os
H
OC
CO
1
Scheme 1. Formula of catalyst Os3(CO)10(H)2 (1).
H
OH
OOH
O
H2O2
+
+
precatalyst 1
2
3
4
5
CH3
CH3
H2O2
O
OH
Let us assume that the dependence shown in Fig. 4(A)
corresponds to the competition for the oxidizing species X
between 1-phenylethanol (6) and a component P of the reaction
mixture:
precatalyst 1
7
Scheme 2. Oxidation of cyclooctane (2) and 1-phenylethanol (6).
6
reagents −−−→ X
X + 6 −−−→ 7
X + P −−−→ products
Wi
k1
(i)
(1)
(2)
than parameters determined for the systems oxidizing without
the participation of reactive radicals (entries 9–12).
k2
c
Appl. Organometal. Chem. 2010, 24, 464–472
Copyright ꢀ 2010 John Wiley & Sons, Ltd.
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G. B. Shul’pin et al.
Table 1. Selectivity parameters in H2O2 oxidations of alkanes by certain catalytic systemsa
C(1) : C(2) : C(3) : C(4)
1◦ : 2◦ : 3◦
trans/cis
Entry
Catalytic system
n-Heptane
MCH
Isooctane
cis-1,2-DMCH
trans-1,2-DMCH
1
2
1
1 : 6.5 : 7 : 6
1 : 10 : 7 : 6
1 : 6.5 : 18
1 : 2 : 6
1 : 5 : 12
0.9
0.9
0.9
1.0
1.2
0.8
hνb
b
3
Fe(SO4)2
1 : 5 : 5 : 4.5
1 : 6 : 7 : 5
1 : 3 : 6
1.3
4
VO3−/PCAc
Ni(ClO4)2/Ld,e
1 : 9 : 37
1 : 4 : 9
0.75
5
1 : 6 : 7 : 6
1 : 7 : 15
1 : 2 : 4
f
6
Al(NO3)3
1 : 5 : 5 : 5
1 : 6 : 23
1 : 4 : 7
0.8
0.9
0.9
0.8
0.9
0.9
g
7
Al2O3
Ti-MMM-2h
1 : 4.5 : 4 : 3.5
1 : 9 : 7 : 6.5
1 : 35 : 25 : 23
1 : 46 : 35 : 34
1 : 14 : 13 : 12
1 : 14 : 9 : 13
1 : 80 : 193 : 100
1 : 9 : 18
1 : 4 : 7
8
1 : 6 : 113
1 : 116 : 255
1 : 26 : 200
1 : 0.3 : 06
1 : 4 : 30
1 : 10 : 240
1 : 5 : 50
1 : 0.4 : 32
1 : 0 : 41
no products
i
9
NaAuCl4
10
11
12
13
[Mn2L2(O)3]2+/MeCO2Hd,j
0.34
0.2
4.1
7.3
k,l
[Mn2L2(O)3]2+/(COOH)2
k,m
Cu(NCCH3)4BF4
TS-1n
no products
no products
no products
a Parameter C(1) : C(2) : C(3) : C(4) is relative normalized (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 n-octane or n-heptane. Parameter 1◦ : 2◦ : 3◦ is relative normalized reactivities of hydrogen
atoms at primary, secondary and tertiary carbons of methylcyclohexane and isooctane. Parameter trans/cis is the ratio of isomers of tert-alcohols
with mutual trans- and cis-orientation of the methyl groups formed in the oxidation of cis- and trans-1,2-dimethylcyclohexane. All parameters were
measured after reduction of the reaction mixtures with triphenylphosphine before GC analysis and calculated based on the ratios of isomeric alcohols.
b See Shul’pin et al.[7a]
c For this system, see Kozlov et al.[2t] and Shul’pin et al.[7b–e]
d L is 1,4,7-trimethyl-1,4,7-triazacyclononane.
e For this system, see Shul’pin et al.[7f]
f For this system, see Mandelli et al.[7g]
g For this system, see Mandelli et al.[7h]
h For this system, see Bonon et al.[2g]
i For this system, see Shul’pin et al.[7i]
j For this system, see Shul’pin et al.[2d,p 7j,k]
k tert-Butylhydroperoxide is used instead of H2O2.
l For this system, see Shul’pin et al.[7l,m]
m For this system, see Shul’pin et al.[7n]
n For this system, see Shul’pin et al.[7o,p]
R'=O
ROH
W1
H2O2
"Os=O" + O2 + H2O + H+
1
"Os=O"
RH
H2O2
H2O2
"Os−OOH"
.
"Os=O" + HO
RH W2
.
ROOH
R
Scheme 3. Proposed reaction pathways in the oxidation of alkane RH and alcohol ROH with hydrogen peroxide catalyzed by complex 1.
where Wi is the rate of generation of species X by the catalytic
system.
The analysis of this kinetic scheme leads to equation (3):
and equation (3), it follows that k2[P]/k1 = 0.6. Assuming that P
is acetonitrile (for its oxidation[9]), we calculate k2/k1 = 0.035. If
we assume that P is hydrogen peroxide this ratio is k2/k1 = 0.3.
The k2/k1 ratios are 7 × 10−4 and 2.5 × 10−3 for the interac-
tions of acetonitrile and hydrogen peroxide, respectively, with
hydroxyl radicals. It can be seen that in our case both values are
substantially higher (50 and >120 times, respectively) than the
corresponding k2/k1 ratios for the reactions with the participation
of hydroxyl radicals. These calculations support again that the
d[6]
dt
d[7]
dt
Wi
k2[P]
−
=
=
(3)
1 +
k1[6]
Equation (3) satisfactorily describes the experimantally ob-
tained data (see Fig. 4B). From the dependence shown in Fig. 4(B)
c
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Copyright ꢀ 2010 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. 2010, 24, 464–472

Oxidation of alkanes and alcohols with hydrogen peroxide
A
100
80
60
40
20
1
60
40
W
2
20
0
0
0
0.5
1.0
1.5 2.0
2.5
3.0
103 [1]0 / M
0
0
0
5
10
10
10
15
15
15
Figure 3. Dependence of the initial rate of acetophenone accumulation in
the oxidation of 1-phenylethanol on the initial concentration of catalyst 1.
Conditions: [1-phenylethanol]0 = 1.6 M, [H2O2]0 = 2.0 M, [H2O]total = 7.2
M, 60 ◦C.
B
100
80
60
40
20
2
B
4
1
W
2
8
0
0
6
4
2
0
0
5
10
5
1
/ M−1
W
[6]0
C
A
100
80
1
60
0
0.4
0.8
1.2
1.6
[1-phenylethanol]0 / M
40
20
0
2
Figure 4. Dependence of the initial rate of acetophenone accumulation
in the oxidation of 1-phenylethanol on the initial concentration of
1-phenylethanol. Conditions: [H2O2]0 = 2.0 M, [H2O]total = 7.2 M,
[1]0 = 5 × 10−4 M, 60 ◦C.
5
Time / h
Figure 2. Consumption of 1-phenylethanol (curve 1) and accumula-
tion of acetophenone (curve 2) in the oxidation of 1-phenylethanol
with H2O2 catalyzed by complex 1 under different conditions. (A)
[1-phenylethanol]0 = 1.6 M, [H2O2]0 = 2.0 M, [H2O]total = 7.2 M,
[1]0 = 5 × 10−4 M. (B) [1-phenylethanol]0 = 0.4 M, [H2O2]0 = 1.0 M,
[H2O]total = 3.6 M, [1]0 = 5 × 10−4 M. (C) [1-phenylethanol]0 = 0.4 M,
[H2O2]0 = 2.0 M, [H2O]total = 7.2 M, [1]0 = 5 × 10−4 M. The solvent was
acetonitrile (total volume of the reaction solution was 5 ml), 60 ◦C.
[H2O]added / M
0
5
10
15
10
W
5
0
main species inducing the 1-phenylethanol oxidation is not the
hydroxyl radical.
0
5
10
[H2O]total / M
15
Some decrease of W0 at [H2O2]0 > 1.5 M is apparently due to
the concurrent interaction of species X with 1-phenylethanol and
hydrogen peroxide. In accordance with proposed kinetic scheme
which is reflected by equation (3) and the data shown in Fig. 4, the
1-phenylethanol oxidation rate W0 should decrease by 1.2 times
when [H2O2]0 increases from 1.5 to 3.0 M. As Fig. 6 shows that this
decrease of W0 is approximately equal to 1.25, we can conclude
Figure 5. Dependence of the initial rate of acetophenone accumulation
in the oxidation of 1-phenylethanol on the concentration of water.
Conditions: [1-phenylethanol]0 = 1.6 M, [H2O2]0 = 1.0 M, [1]0 = 5 × 10−4
M, 60 ◦C.
c
Appl. Organometal. Chem. 2010, 24, 464–472
Copyright ꢀ 2010 John Wiley & Sons, Ltd.
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G. B. Shul’pin et al.
Experimental
15
10
5
Triosmium carbonylhydride, H2Os3(CO)10 (precatalyst 1; for syn-
thesis and properties of this compound, see ref.[11]) was used in
the form of a stock solution in acetonitrile (typically, concentration
[1]0 in the stock solution was 10−3 M). The reactions of alkanes or
1-phenylethanol were typically carried out in air in thermostated
Pyrex cylindrical vessels with vigorous stirring and using MeCN
as solvent. Precatalyst 1 was introduced into the reaction mix-
ture in the form of a stock solution in acetonitrile. The substrate
(alkane or 1-phenylethanol) was then added and the reaction
started when hydrogen peroxide (50% in H2O) was introduced in
one portion. (CAUTION: compound 1 is toxic and should there-
fore be handled with care. All reactions should be carried out in
a fume hood. The combination of air or molecular oxygen and
H2O2 with organic compounds at elevated temperatures may be
explosive!) After certain time intervals samples (about 0.2 ml) were
taken.
W
0
0
1
2
3
[H2O2]0 / M
Figure 6. Dependence of the initial rate of acetophenone accumulation
in the oxidation of 1-phenylethanol on the initial concentration of
hydrogen peroxide at constant concentration of water. Conditions:
[1-phenylethanol]0 = 1.6 M, [1]0 = 5 × 10−4 M, [H2O]total = const = 10.8
M, 60 ◦C.
The reactions with alkanes were stopped by cooling and after
addition of nitromethane as a standard compound analyzed
by GC. In order to determine concentrations of all alkane
(cyclooctane)oxidationproductsthesamplesof reactionsolutions
wereanalyzedtwice(beforeandaftertheirtreatmentwithPPh3)by
GC (Chromatograph-3700, fused silica capillary column FFAP/OV-
101 20/80 w/w, 30 m × 0.2 mm × 0.3 µm; helium as a carrier gas)
that our assumption about the concurrent interaction of X with
1-phenylethanol and H2O2 is supported by the experimental data.
Fourthly, the oxidation rate of 1-phenylethanol is 5–10 times
higherthantherateofcyclooctaneoxidationcatalyzedby1.Taking
into account all features discussed above, we can assume that
during hydrogen peroxide decomposition catalyzed by complex
1 oxidizing species of two different types are generated with
different rates. One of these species is hydroxyl radical, which
oxidizes alkanes. Another species is apparently an osmyl species
containing Os O bonds. This species is much less reactive in
comparison with hydroxyl radical and it is unable to efficiently
attack alkanes, RH, but it can react with an alcohol, ROH. The
generation rate of the osmyl species is 5–10 times higher than
the generation rate of hydroxyl radical. Based on this model of
our oxidizing system (Scheme 3), we can say that the selectivity
parameters of alkane oxidation are governed by the reaction with
hydroxyl radicals whereas the rate of 1-phenylethanol oxidation
as well as the yield of the products are limited mainly by the
process of the osmyl species generation (W1/ W2 > 5). There
is also some interaction between 1-phenylethanol and hydroxyl
radicals. However the increment of this pathway into the total
oxidation process is not substantial; the dominating route is with
the participation of the ‘Os O’ species.
measuring concentrations of alkanol and alkanone. For details
[1a,f,g]
of this method developed previously,
see the Appendix.
Authentic samples of all oxygenated products were used to
attribute the peaks in chromatograms (comparison of retention
times was carried out for different regimes of GC-analysis). Blank
experiments showed that, in the absence of precatalyst 1, only
very low amounts of products were formed.
Concentrations of products obtained in the oxidation of
1-phynylethanol, benzene and styrene after certain time inter-
vals were measured using 1H NMR method (acetone-d6 was added
to the samples; ‘Bruker AMX- 400’ instrument, 400 MHz). For the
determinationofconcentrationsofsubstratesandproducts, corre-
sponding signals were integrated using added 1,4-dinitrobenzene
as a standard.
Acknowledgment
Scheme 3 reflects the competition between 1-phenylethanol
and hydrogen peroxide for the primary oxidizing species ‘Os O’,
which is generated by the catalytic system. Species ‘Os O’ is
a derivative of low-valence (II, III or IV) osmium formed from
1 under the action of H2O2, and it is possibly stabilized by
acetonitrileligands.Similarspecieshavebeenrecentlysynthesized
and characterized.[10] This scheme takes into account also
the formation of hydroxyl radicals in the course of further
transformations of the ‘Os O’. These further steps of the reaction
induce the oxidation of alkanes but they do not play a crucial
role in the alcohol oxidation due to low rate of hydroxyl radical
generation.Theschemealsoconsidersthecatalasedecomposition
of hydrogen peroxide which is substantial at low concentration of
1-phenylethanol.
This work was supported by the Russian Foundation for Basic
Research (grant no. 06-03-32344-a).
Supporting information
Supporting information may be found in the online version of this
article.
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Conclusions
This study demonstrates that oxidations of alkanes and alcohols
by the 1–H2O2 system proceed via different mechanisms with
participation of either hydroxyl radicals or osmyl species ‘Os O’.
c
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Copyright ꢀ 2010 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. 2010, 24, 464–472

Oxidation of alkanes and alcohols with hydrogen peroxide
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Copyright ꢀ 2010 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. 2010, 24, 464–472

Oxidation of alkanes and alcohols with hydrogen peroxide
Appendix: Estimation of Amounts of Alkyl
Hydroperoxide, Alcohol, and Ketone or Alde-
hyde by a Gc Method Using Triphenylphos-
phine and Pyridine
sum obtained after the reduction. However, in some cases (when
the extensive decomposition of various peroxides occurs in the
injector before the reduction) the sum of concentrations alcohol +
ketone before the reduction is lower than that obtained after the
reduction. It is evidently, that the analysis after the reduction gives
more precise quantification of products because PPh3 reduces
ROOH to ROH quantitatively. Also in some cases (quartz-lined
injector and silica capillary columns of GC instrument) peaks of
the alkyl hydroperoxide can be detected in addition to the peaks
of the alcohol and ketone. However, the peaks of ROOH can be
observed only very seldom when the hydroperoxide decomposes
only partly (this is possible if the injector is free from the traces of
the catalyst used in the oxidation; after two or three injections the
accumulated in the injector catalyst begins to decompose ROOH
completely).
Oxygenation of alkanes by molecular oxygen or peroxides in air
usually gives rise to the formation of the corresponding alkyl
hydroperoxides as the main primary products. The quantification
of alkyl hydroperoxides and ketones (aldehydes) and alcohols
present in the reaction solution can be performed by a simple GC
method which uses tryphenylphosphine. This method has been
developed earlier.[1a,f,g]
Alkyl hydroperoxides formed in various oxidations of alkanes
by O2 or H2O2 are decomposed in the chromatograph to afford
correspondingalcoholsandketones(aldehydes)asmainproducts:
Thus, determination of a sum of concentrations alcohols +
ketone (aldehyde) after reduction with PPh3 gives us precise value
of total concentration of all primary products (that is of alkyl
hydroperoxide, alcohol and ketone). The comparison of this value
with concentrations of the alcohol and ketone (aldehyde) before
reduction with PPh3 allows us to estimate the real concentrations
of the alkyl hydroperoxide, alcohol and ketone (aldehyde) in the
reaction solution. It should be noted that it is incorrect to make
any conclusions on the existence or non-existence of the alkyl
hydroperoxide on the basis of the chromatogram obtained only
afterthereductionwithPPh3.Indeed,intheabsenceofROOHinthe
reactionmixtureallamountofthealcoholdeterminedbyGCcould
be equal to the real amount of the alcohol present in the reaction
solution. If the amounts of the alcohol and ketone determined
before PPh3 reduction are exactly equal to the amounts measured
after reduction this fact testifies that no alkyl hydroperoxide is
present in the reaction solution.
RꢁCH(OOH)Rꢁꢁ −−−→ RꢁCH(OH)Rꢁꢁ + RꢁC( O)Rꢁꢁ + . . .
(A1)
The alcohol/ketone (aldehyde) ratio is usually around 1 : 1. The
exact value of this ratio depends on the construction of the
injector, its material, temperature of the injector, etc. It depends
also on the nature and amount of the catalyst used in the oxidation
reaction as this catalyst is injected in a very small amount into the
instrument. Many reactions between the components can occur
in the injector. Decomposition of ROOH produces not only the
alcohol and ketone but also affords various derivatives obtained
in the C–C bond rapture processes. The reaction of the products
with non-consumed in the reaction H2O2 is also possible in the
injector. As a consequence, the chromatogram shows many small
peaks in addition to the main peaks of the alcohol and ketone.
As mentioned above, typically alkyl hydroperoxide decomposes
in the gas chromatograph to afford the corresponding alcohol
and ketone (aldehyde) in the ca 1 : 1 ratio. However, under specific
conditions, this ratio can be substantially different. For example, if
pyridine is present in the reaction mixture this base induces the
transformation of the hydroperoxide into ketone:
How can we estimate quantitatively concentrations of alkyl
hydroperoxide, ROOH, alcohol, ROH, and ketone or aldehyde,
RꢁC( O)Rꢁꢁ formed in the oxidation of alkane, RH? Let us suppose
that real concentrations of the three products in the reaction
sample are the following:
[ROOH] = xreal
,
N-base
R'CH(OOH)R″
R'C( O)R″
+ H2O
(A2)
[ROH] = yreal
,
[RꢁC( O)Rꢁꢁ] = zreal
,
As a result the ketone : alcohol ratio can be raised to 8 : 1 (see
Fig. S1a in ref.[5b]).
If an excess of solid PPh3 is added to a sample of the reaction
solution ca 10 min before GC analysis the alkyl hydroperoxide,
ROOH, present in the reaction mixture is completely reduced to
the corresponding alcohol:
that is, the oxidation of RH gives the followong real concentrations
of the products:
ROOH ROH RꢁC( O)Rꢁꢁ
RH −−−→
+
+
(A4)
xreal
yreal
zreal
Now we should introduce some restrictions: (i) no reaction oc-
curs between H2O2 and RH in the injector of chromatograph; (ii)
the alkyl hydroperoxide is completely decomposed in chromato-
graph giving only additional portions of the alcohol and ketone
(aldehyde).
If we inject the sample directly into chromatograph all really
present in the solution alkyl hydroperoxide is decomposed to give
detectable by GC additional concentrations yadd and zadd of ROH
and RꢁC( O)Rꢁꢁ:
RꢁCH(OOH)Rꢁꢁ + PPh3 −−−→ RꢁCH(OH)Rꢁꢁ + O PPh3
(A3)
In this case, 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).
The phosphine reduces not only ROOH but also oxidizing
reagent (H2O2) and thus no parasite oxidation reactions become
possible in the injector. In addition, the phosphine reduces
all primary product|s of the peroxidic nature, and due to this
reduction no products obtained in the injector via decomposition
of peroxidic compounds are seen. In many cases (if in the injection
before the reduction only small amounts of peroxides give
products of various rearrangements) the sum of concentrations
alcohol + ketone before the reduction is equal to the same
ROOH
ROH RꢁC( O)Rꢁꢁ
−−−→
+
(A5)
xreal
yadd
zadd
As we discussed above, the yadd/zadd ratio depends on the
material of the chromatograph and conditions of the GC analysis,
c
Appl. Organometal. Chem. 2010, 24, 464–472
Copyright ꢀ 2010 John Wiley & Sons, Ltd.
www.interscience.wiley.com/journal/aoc

G. B. Shul’pin et al.
inlcuding the influence of some components of the reaction
solution, especially of a catalyst. Let us suppose that
Using the last equations we can easily deduce formulae for
the real concentrations of the three products expressed via
concentrations of the alcohol and ketone measured before and
after reduction with PPh3:
yadd
= m
(A6)
zadd
[ROOH] = xreal = m(zbefore − zafter) + (yafter − ybefore) (A23)
Parameter m can be measured experimentally via injection of
a solution of pure specially synthesized ROOH under identical
conditions. Concentrations of the alcohol and ketone (aldehyde)
measured by GC before reduction with PPh3 will be the following:
[ROH] = yreal = ybefore − m(zbefore − zafter
)
(A24)
[RꢁC( O)Rꢁꢁ] = zreal = zafter
(A25)
If we assume (or determine experimentally) that m ≈ 1 we will
obtain a simple formulae:
ybefore = yreal + yadd
zbefore = zreal + zadd
(A7)
(A8)
[ROOH] = xreal ≈ (zbefore − zafter) + (yafter − ybefore
)
(A26)
(A27)
(A28)
[ROH] = yreal ≈ ybefore − (zbefore − zafter
)
In the case when we reduce the sample with PPh3 after this
procedure taking into account reaction (A9)
[RꢁC( O)Rꢁꢁ] = zreal = zafter
ROOH
ROH
Taking into account the ability of alkyl hydroperoxides to
decompose in the chromatograph in the presence of pyridine (see
Fig. S1a in Shul’pin et al.[5b]) to produce mainly or exclusively the
corresponding ketone or aldehyde we can propose an alternative
methodforestimationofrealconcentrationsofthethreeproducts,
ROOH, ROH and RꢁC( O)Rꢁꢁ. This method allows us to avoid the
determination of parameter m in equation (A6). Let us consider
again reactions (A29 ≡ A2) and (A30 ≡ A9):
+ PPh3 −−−→
(A9)
∗
xreal
yadd
and expression (A10)
∗
yadd = xreal
(A10)
the GC analysis will give the following measured concentrations:
∗
yafter = yreal + yadd = yreal + xreal
zafter = zreal
,
(A11)
(A12)
pyridine
(A29)
(A30)
R'CH(OOH)R″
R'C( O)R″ + H2O
zadd
In summary, we have the following system of equations:
xreal
*
ROOH
ROH
ybefore = yreal + yadd
zbefore = zreal + zadd
yafter = yreal + xreal
zafter = zreal
(A13)
(A14)
(A15)
(A16)
+ PPh3 −−−→
+ OPPh3
∗
yadd
xreal
The GC analysis of the reaction mixture which contains
pyridine gives us measured concentrations of the alcohol and
ketone ywith−py and zwith−py. Assuming that reaction (A29) is the
quantitative transformation of the alkyl hydroperoxide to the
ketone in chromatograph in the presence of pyridine and reaction
(A30) is the quantitative reduction of ROOH by PPh3 we will come
to the following equations:
yadd
= m
zadd
(A17)
Subtracting equation (A16) from equation (A14) we obtain the
expression
zbefore − zafter = zadd
Taking into account that
(A18)
ywith−py = yreal
(A31)
(A32)
(A33)
(A34)
∗
zwith−py = zreal + zadd = zreal + xreal
∗
yafter = yreal + yadd = yreal + xreal
zafter = zreal
yadd = mzadd
(A19)
we come to equations (A20) and (A21≡A15).
Now we can easily obtain the equations which allow us to
calculate real concentrations of the three products:
ybefore = yreal + mzadd = yreal + m(zbefore − zafter
yafter = yreal + xreal
)
(A20)
(A21)
[ROOH] = xreal = zwith−py − zafter = yafter − ywith−py (A35)
Subtracting equation (A21) from equation (A20) we obtain
ybefore − yafter = m(zbefore − zafter) − xreal (A22)
[ROH] = yreal = ywith−py
(A36)
[RꢁC( O)Rꢁꢁ] = zreal = zafter
(A37)
c
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Copyright ꢀ 2010 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. 2010, 24, 464–472