Synthesis of μ-oxo-bisiron(III)porphyrin compounds and their catalysis for cyclohexane hydroxylation

Article abstract of DOI:10.1006/jcat.1998.2138

Fourteen substituted μ-oxo-bis[tetraphenylporphinatoiron(III)] derivants ([TXPPFe^III]₂O) were synthesized by passing chlorotetraphenylporphinatoiron(III) (TPPFe^IIICl) through a neutral alumina chromatographic column, and nine of which were used in cyclohexane hydroxylation with PhIO as a new type of catalyst under moderate conditions. The experiments have shown that the yields, rate constants k of the cyclohexane hydroxylation have a linear relationship to characteristic constants σ of substituents on porphyrin rings, a physical constant characterizing the electronic effects and steric effects of a substituent group, and that the product distributions and kinetic properties of the reactions are dependent on the reaction temperature, solvent as well as air. In contrast with monoironporphyrin TPPFe^IIICl, μ-oxo-bisironporphyrin [TPPFe^III]₂O is shown to have the better catalytic power for cyclohexane hydroxylation with PhIO under moderate conditions and stability to PhIO. The research results show that μ-oxo-bisironporphyrin can be used as the model compound of cytochrome P-450 monooxygenase.

Full text of DOI:10.1006/jcat.1998.2138

JOURNAL OF CATALYSIS 178, 182–187 (1998)
ARTICLE NO. CA982138
Synthesis of �-Oxo-bisiron(III)Porphyrin Compounds and Their Catalysis
for Cyclohexane Hydroxylation
1
Can-Cheng Guo
College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082, China
Received December 4, 1997; revised April 16, 1998; accepted April 28, 1998
erate conditions. We found that the yields and rate con-
Fourteen substituted �-oxo-bis[tetraphenylporphinatoiron(III)] stants of the cyclohexane hydroxylation have a linear re-
III
derivants ([TXPPFe ]2O) were synthesized by passing chloro- lationship with the constants of substituents on porphyrin
III
tetraphenylporphinatoiron(III) (TPPFe Cl) through a neutral alu-
rings and that the product distributions and kinetic prop-
erties of the reactions connected with the reaction tem-
mina chromatographic column, and nine of which were used in
cyclohexane hydroxylation with PhIO as a new type of catalyst
perature, solvent as well as air. The study showed that
under moderate conditions. The experiments have shown that the
yields, rate constants k of the cyclohexane hydroxylation have a
linear relationship to characteristic constants � of substituents on
porphyrin rings, a physical constant characterizing the electronic
effects and steric effects of a substituent group, and that the prod-
uct distributions and kinetic properties of the reactions are depen-
III
�
-oxo-bisironporphyrin [TPPFe ]2O has better catalytic
power for cyclohexane hydroxylation with PhIO under
moderate conditions and is more stable than monoironpor-
III
phyrin TPPFe Cl. The research results show that �-oxo-
bisironporphyrin can be used as the model compound of
dent on the reaction temperature, solvent as well as air. In con- cytochrome P-450 monooxygenase.
III
trast with monoironporphyrin TPPFe Cl, �-oxo-bisironporphyrin
III
[
TPPFe ]2O is shown to have the better catalytic power for cy-
EXPERIMENTAL
Instruments and Reagents
clohexane hydroxylation with PhIO under moderate conditions
and stability to PhIO. The research results show that �-oxo-
bisironporphyrin can beused asthemodelcompound ofcytochrome
P-450 monooxygenase.
�c 1998 Academic Press
UV-Vis spectra were obtained with a Perkin Elmer
L-17 UV-Vis spectrophotometer; Perkin-IR spectra were
recorded on a Elmer model 783 IR spectrophotometer. GC
analysis was performed on a Shimadzu GC-16A gas phase
chromatography flame ionization instrument. A Perkin-
Elmer 2400 elementary analyser and a Shanghai mini-
motor plant model 5012 constant temperature water-bath
were used.
Key Words: porphyrin; catalyze; oxidation.
INTRODUCTION
In 1978, Groves first reported that chlorotetraphenylpor-
III
phinatoiron(III) (TPPFe Cl) could catalyze the activity
of the inert hydrocarbon bond as a model of cytochrome
P-450 monooxygenase (1). The behavior of metallopor-
phyrins catalyzing the activity of the inert hydrocarbon
bond is just the same as that of cytochrome P-450 monooxy-
genase in biological phenomena, of which many scien-
tists are strongly interested (2). In order to obtain in-
sight into the possibility of �-oxo-bisiron(III)porphyrin
compounds to catalyze the inert hydrocarbon bond,
we prepared 14 �-oxo-bis[tetraphenylporphinatoiron(III)]
Before being used, benzene and dichloromethane were
dehydrated; neuteral Al2O3 was baked 5 h at 100 C; pyr-
�
role and benzaldehyde were redistilled. All reagents were
analytically pure or chemically pure as received.
III
TXPPH2 and TXPPFe Cl were synthetized according
to the documented procedures (3, 4). Their structures were
confirmed by elementary analysis, IR spectra, and UV-Vis
spectroscopy. PhIO was synthetized by documented proce-
dures (5), and the purity measured by iodimetry was 99% .
III
derivants [TXPPFe ]2O, shown in Fig. 1, with chlorote-
III
III
traphenylporphinatoiron(III) (TPPFe Cl) through a neu- Synthesis of [TXPPFe ] O
2
tral alumina chromatographic column, and nine of which
were used to catalyze the oxidation of cyclohexane into
cyclohexanol and cyclohexanone with PhIO under mod-
A typical procedure is described as follows: 2 g of
TPPFe Cl was passed through a chromatographic column
III
filled with 500 g Al2O3 using the wet method. Benzene con-
taining 5% of C2H5OH was used as a drip washing liquid.
1
III
E-mail: ccguo@mail.hunu.edu.cn.
[TPPFe ]2O was formed in the above procedure. Effluent
182
0021-9517/98 $25.00
Copyright �c 1998 by Academic Press
All rights of reproduction in any form reserved.

�
-OXO-BISIRON(III)PORPHYRIN COMPOUNDS
183
FIG. 1. Structure of 14 [TXPPFeIII]2O. 1. R1 = R2 = R3 = H; 2. R1 = CH3, R2 = R3 = H; 3. R1 = Cl, R2 = R3 = H; 4. R1 = i-C3H7, R2 = R3 = H;
. R1 = F, R2 = R3 = H; 6. R1 = Br, R2 = R3 = H; 7. R1 = I, R2 = R3 = H; 8. R1 = H, R2 = F, R3 = H; 9. R1 = H, R2 = Cl, R3 = H; 10. R1 = H, R2 = Br,
5
R3 = H; 11. R1 = H, R2 = CH3, R3 = H; 12. R1 = R2 = H, R3 = F; 13. R1 = R2 = H, R3 = Cl; 14. R1 = R2 = H, R3 = Br.
was evaporated to dryness under reduced pressure. The unless otherwise specified. A solution of PhIO (100 mg
III
� 4
III
� 6
purity of [TPPFe ]2O was checked with HPLC or IR. 4.5 � 10 mol), [TPPFe ]2O (10 mg 7.5 � 10 mol) and
If the components with the retention time 2.87 min of cyclohexane (5mL) in benzene (5mL) waswarmed to 303K
TXPPFe Cl in HPLC, or the absorption band at 380 cm
III
� 1
using circulating water and stirred 2 h with an electromag-
(
�Fe–Cl) in IR disappeared, the reactants were thought to be netic stirrer. The products were analysed by gas chromatog-
transformed completely. Otherwise, the above-mentioned raphy. Yields were calculated based on the input moles of
III
procedure was repeated until TPPFe Cl was transformed PhIO. Samples were collected from reactant system with a
III
III
completely into [TPPFe ]2O. Fourteen [TXPPFe ]2O micro-injector regularly to do dynamics analyses. Quanti-
compounds, shown in Fig. 1, were synthesized in the same tation calculations used an internal standard method. The
procedure. Their elementary analysis, IR, and UV-Vis max- standard material was chlorobenzene.
imum are listed in Table 1.
III
Oxidation of [TXPPFe ]2O with PhIO
Cyclohexane Hydroxylation with PhIO
PhIO was dissolved in benzene. Its concentration was
Cyclohexane hydroxylation in this paper was carried out determined by iodimetry. Accurately weighed metallo-
under a nitrogen atmosphere in the following procedures porphyrin in a volumetric flask was diluted to about
TABLE 1
Data of Element Analyses, �max, and �Fe–O–Fe of [TXPPFeIII]2O
Element analyses
C
H
N
Compd.
no.
�max
�
1
Found
Calcd.
Found
Calcd.
Found
Calcd.
benzene/nm
�Fe–O–Fe/cm
1
2
3
4
5
6
7
8
9
0
1
2
3
4
78.09
78.23
64.73
79.27
69.81
52.83
45.13
70.01
64.52
52.95
78.33
71.02
64.35
52.45
78.11
78.68
64.90
79.61
70.58
53.26
44.76
70.58
64.90
53.26
78.68
70.58
64.90
53.26
4.23
4.86
2.88
6.25
2.95
2.08
2.26
2.95
2.78
2.13
4.85
3.15
3.13
2.05
4.17
4.95
2.97
6.20
3.21
2.44
2.03
3.21
2.97
2.44
4.95
3.21
2.97
2.44
8.05
7.66
7.11
6.64
7.74
5.35
4.95
7.61
7.03
6.02
7.68
7.63
7.05
5.35
8.28
7.68
6.88
6.63
7.49
5.65
4.77
7.49
6.88
5.65
7.68
7.49
6.88
5.65
407.6, 570.0, 611.2
409.2, 572.8, 612.8
408.0, 570.8, 611.2
409.6, 572.4, 613.6
408.0, 570.0, 610.8
870, 895
870, 895
870, 895
870, 895
875, 895
872, 893
878, 890
880, 905
880, 910
880, 910
885, 920
870, 895
870, 894
868, 893
405.6, 568.4, 607.2
407.6, 568.8, 608.8
408.0, 569.4, 611.4
406.4, 570.4, 610.4
410.5, 571.3, 610.8
409.7, 569.9
1
1
1
1
1
420.9, 572.3

1
1
84
CAN-CHENG GUO
�
5
� 3
0
mol � dm with benzene. After the PhIO and metallo-
porphyrins were mixed at 298 K, the time-variation of the
Soret absorption intensity of [TXPPFe ]2O in the reaction
III
system was measured immediately by UV-Vis spectropho-
tometery.
RESULTS AND DISCUSSION
III
Syntheses and Spectral Characteristics of [TXPPFe ]2O
III
Fleischer et al. (6) synthesized [TPPFe ]2O by the reac-
III
tion of TPPFe Cl with 40% NaOH, but this method gave
only a poor yield and a not so pure product. It was discov-
ered by moniting the reactant system with HPLC that metal
ions fell off in the course of this reaction, so the method
III
was modified in this paper. Thus, TPPFe Cl can change to
III
[
TPPFe ]2O (7) with a good yield (98% ) and puritybypass-
FIG. 2. Change of cyclohexanol concentration c with reaction time t
at different temperatures. Catalyst: [TPPFe ]2O; solvent: benzene; tem-
III
ing it through a neutral Al2O3 chromatographic column.
The procedure is easy to operate. The preparation of all perature: 1, 321 K; 2, 316 K; 3, 311 K; 4, 306 K; 5, 301 K.
4 �-oxo-bis[tetraphenylporphinatoiron(III)] compounds
1
between the quantity of cyclohexanol and reaction time,
and the reaction indicates a zero-order feature in initial
stages. Reaction rates decrease in the latter stages of reac-
tion (Fig. 2).
shown in Fig. 1 can be easily accomplished by this modified
method.
It can be seen from Table 1 that, compared with
III
TXPPFe Cl, there exist the characteristic absorptions at
�
1
III
The above-mentioned dynamicsrelationship doesnot ex-
ist when reactions are carried out in air, and the propor-
tion of cyclohexanone in the reaction products increases
clearly. Reaction temperature, reaction solvent, and sub-
8
70 and 895 cm in the IR spectrum of [TXPPFe ]2O,
which are consistent with the Fe–O–Fe stretching contract
vibration reported in (6). IR analyses of compounds 1–14
indicate that the change of the substituting group on por-
phyrin benzene rings has little influence on the character-
istic absorption of the Fe–O–Fe bonds.
III
stituent groups X of [TXPPFe ]2O have a regular effect
on product rates and the kinetics of the reaction.
III
III
Fe atoms of [TXPPFe ]2O and TXPPFe Cl are in the
5
5
Influence of Reaction Temperature
d configuration. The high-spin d feature is observed from
ESR of TXPPFe Cl at room temperature, but is un-
observed in [TXPPFe ]2O. Probably this is because of
antiferromagnetic coupling between two Fe atoms of
III
Figure 2 shows the changes of cyclohexanol concentra-
III
�
3
tion c (mol � dm ) with reaction time t at different tem-
3+
III
peratures in benzene solvent in the case of [TPPFe ]2O
III
[TXPPFe ]2O though the oxygen bridge (8). This supplies
being used as the catalyst. In the range of the test tem-
peratures, the zero-order kinetic relationship between the
reaction product cyclohexanol and reaction time is present.
With temperature variation, the rate, yield, and time needed
to complete the reaction all change. Reaction yield and the
time needed to complete the reaction decrease with increas-
ing the temperature, but the mole ratio of cyclohexanol and
cyclohexanone are hardly affected. The observed rate con-
stant ka obtained from Fig. 2 increases with the increasing
temperature (Table 2). Figure 3 shows that ka and temper-
ature T have an Arrhenius relationship for which the linear
correlation coefficient is 0.9910.
III
further evidence for a �-oxo construction of[TXPPFe ]2O.
There exists a strong Soret absorbance at 410–420 nm in
III
III
UV-Vis spectra of both [TXPPFe ]2O and TXPPFe Cl,
but [TXPPFe ]2O shifts to violet at about 5 nm, compared
with the corresponding TXPPFe Cl. There is no charac-
teristic absorption at 380 nm for [TXPPFe ]2O, but there
III
III
III
III
is for the corresponding TXPPFe Cl.
III
Cyclohexane Hydroxylation Catalyzed by [TXPPFe ]2O
III
Cyclohexane hydroxylation catalyzed by [TXPPFe ]2O
with PhIO is
The mathematics expression is
Ln ka = � 2704/T + 1.9734.
[1]
The reaction productsare cyclohexanoland cyclohexanone.
Influence of Solvent on the Reaction
The influence of solvent on cyclohexane monooxygena-
III
In the absence of [TXPPFe ]2O no cyclohexanol nor cyclo-
III
hexanone was formed, indicating that [TXPPFe ]2O acts
III
as a catalyst in the reaction. There is a linear relationship tion catalysized by [TXPPFe ]2O is remarkable. Table 3

�
-OXO-BISIRON(III)PORPHYRIN COMPOUNDS
185
TABLE 2
Cyclohexane Hydroxylation Results at Different
Reaction Temperatures
Reaction temperature T (K)
301
306
311
316
321
Time t complete reaction (min) 116
85
19.8
5.75
9.04 10.53 12.17 13.14 16.30
7.01 6.86 6.71 6.64 6.42
69
17.2
5.82
57
15.4
5.67
45
13.4
5.42
Cyclohexanol yield (% )
22.0
5.70
Alcohol : ketone (mol ratio)
4
� 1
1
� 1
)
ka � 10 (mol � dm � min
�
ln(ka/mol � dm� � min
� 1
)
Note. Yield is based on inputed PhIO.
lists the results of cyclohexane hydroxylation catalysized by
III
[
TPPFe ]2O with PhIO in five kinds of solvents. In cyclo-
hexane solvent, the products were detected after the reac-
tion was run for 3 h. The rate of this reaction was the lowest,
FIG. 3. Relationship between reaction rate constant ka and temper-
but the reaction yield was the highest. Reaction induction ature T.
periods disappeared, when 0.5 mL benzene was added to
the cyclohexane reaction system, and reaction speed in-
changed for cyclohexane hydroxylation catalyzed by�-oxo-
creased, but the yield decreased. The induction period of
the reaction was not present when other solvents were used.
Table 3 indicates that with the increase of solvent polarity,
the reaction yield decreased, but selectivity of the reaction
converting cyclohexane into alcohol increased. The influ-
ence of solvent polarity on the rate of the reaction is espe-
cially outstanding. Solvent polarity speeds up the reaction
rates. It is found that the reaction yield decreases when
methanol is used as the solvent, probably because a part
of oxidant PhIO is depleted due to the reaction between
PhIO and methanol. The linear relationship between the
product cyclohexanol and reaction time does not exist, and
the proportion of cyclohexanone in the reaction products
is so little that it cannot be checked by gas chromatogra-
phy. In addition, �-oxo-bisiron(III)porphyrin can be partly
transformed into monoiron(III)porphyrin in CH2Cl2 (9),
therefore, no linear relationship between cyclohexanol and
the reaction time was observed when CH2Cl2 was used as
solvent.
bis[tetraphenylporphinatoiron(III)]. Table 4liststhe results
III
of cyclohexane oxidation catalysized by [TPPFe ]2O with
PhIO in the presence of air or nitrogen. In the presence of
air, the total yields of the reaction increased, but selectiv-
ity of the reaction to the product cyclohexanol decreased.
In addition, in the presence of the air, there is not a linear
relationship between the quantity of cyclohexanol and the
reaction time.
III
Influence of Substituting Group X in [TXPPFe ]2O
on the Reaction
Cyclohexane hydroxylation catalyzed by �-oxo-bis
[tetraphenylporphinatoiron(III)] compounds 1–9 with dif-
ferent substitute groups X on the porphyrin ring gives a lin-
ear relationship between cyclohexanol yield and reaction
time t in 2 h after the start of the reaction. But substitute
groups X obviously affect the rate of reaction. Reaction
yield, product distribution, and reaction rate constant kb of
cyclohexane hydroxylation, catalyzed by different substi-
Influence of the Presence of Air on the Reaction
III
tute groups X [TXPPFe ]2O, are listed in Table 5.
In the presence of air, the sum of cyclohexanol and cy-
Experimental results indicated that changing the substi-
clohexanone yields and the ratios of alcohol to ketone tute X on porphyrin rings scarcely affects the proportion
TABLE 3
Result of Cyclohexane Hydroxylation in Different Solvents
Solvent
CH2Cl2
CH3OH
CH3COCH3
C6H6
C6H12
C6H6 + C6H12
Total yield (% )a
14.97
12.80
—
6.54
12.53
7.27
16.80
1
29.13
5.70
9.45
2
62.60
3.64
4.42
16
37.52
4.52
7.45
4
b
Alcohol : ketone (mol ratio)
4
� 1
� 1
ka � 10 (mol � dm � min
)
—
1
Time t complete reaction (min)
2
a
Total yield is the sum of cyclohexanol and cyclohexanone yields.
Mol number of cyclohexanone is lower than the limit of detection.
b

1
86
CAN-CHENG GUO
TABLE 4
Cyclohexane Hydroxylation Results in the Presence of Aira
Total yields (% )
Alcohol : ketone
Air
Nitrogen
20.53
14.97
7.5
12.8
a
The reaction time is 2 h. The reaction solvent is CH2Cl2.
of cyclohexanone and cyclohexanol, but the yield and the
rate of reaction changes regularly. A linear relationship ex-
ists between the characteristic constant � of the substitute
group on the porphyrin ring and the cyclohexanol yield, as
well as the observed rate constant kb (shown in Fig. 4).
The above relationship can be expressed mathematically
as
Cyclohexanol yield (% ) = 16.66� + 25.40
lg kb = 0.318� � 0.6545.
[2]
[3]
FIG. 4. Relationship between substituting group constant � and cy-
clohexanol yield and rate constant kb.
The slope of the line is larger than zero, indicating that
electron-attracting groups make rates and yields of the re-
action increase. This result is consistent with a report by
Tsuchira and Seno (10). In addition, the yield and rate of
reaction are greater than the expected values when the iso-
propyl group or heavy atom Br is introduced to the por-
phyrin benzene ring, which relates well to the facts that a
large group on a porphyrin ring will increase stability of the
porphyrin and raise the reaction yield (11).
III
stants kc of the oxidation of [TXPPFe ]2O by PhIO are
listed in Table 6.
The linear relationship between the substitute group con-
stant � and reaction rate constant kc is
lg k = 0.3973� � 1.5882.
c
[4]
It shows that electron-attracting groups make the rate of
the reaction increase.
III
Oxidation of [TXPPFe ]2O by PhIO
Comparison of the Catalytic Power between
III
[
TXPPFe ]2O can catalyze cyclohexane monooxygena-
III
III
[
TPPFe ]2O and TPPFe Cl
III
tion with PhIO, but alternately, [TXPPFe ]2O also can
be oxidized by PhIO and lose catalytic power. The spec-
III
III
Both [TPPFe ]2O and TPPFe Cl can catalyse cyclo-
III
trum absorption of [TXPPFe ]2O in the visible region dis- hexane hydroxylation, and the products are also the same,
appeared when PhIO is present, which indicates that the but their catalytic powers have obvious differences. The re-
�
-electron conjugation system of porphyrin has been de- sults of cyclohexane hydroxylation catalyzed separately by
III
III
III
stroyed. Kinetics of oxidation of [TXPPFe ]2O by PhIO in [TPPFe ]2O and TPPFe Cl are listed in Table 7.
III
III
dichloromethane is complicated because [TXPPFe ]2O is
Compared with TPPFe Cl, the yields of the reaction
III
transformed into monoiron(III) porphyrin and undergoes catalyzed by [TPPFe ]2O are higher, but the rates of reac-
oxidation of the porphyrin ring, but the reaction shows first- tion are clearly lower. The reaction catalyzed by TPPFe Cl
III
order dynamic reaction features in benzene. The rate con- has no induction period in cyclohexane, but the reaction by
TABLE 5
Result of Cyclohexane Hydroxylation Catalyzed by Different [TXPPFeIII]2O Catalysts
Catalyst
X
1
H
2
p-F
3
p-Cl
4
5
6
m-F
7
p-Cl
8
9
p-CH3
p-(i-Pr)
m-Br
m-CH3
�
0
0.06
25.95
5.89
0.233
0.633
0.23
28.50
5.95
0.265
0.577
� 0.17
22.10
5.98
0.199
0.702
� 0.15
24.53
5.71
0.189
0.723
0.34
30.50
5.90
0.287
0.542
0.37
31.83
5.91
0.295
0.530
0.39
33.00
5.87
0.283
0.548
� 0.07
24.00
5.76
0.213
0.671
Cyclohexanol yield (% )
Alcohol : ketone (mol ratio)
kb (min
�
24.80
5.70
0.225
0.647
�
1
)
lg (kb/min 1)
�

�
-OXO-BISIRON(III)PORPHYRIN COMPOUNDS
187
TABLE 6
Rate Constant kC of the Oxidation of [TXPPFeIII]2O with PhIO
[
TXPPFeIII]2O
1
2
3
4
5
6
7
8
9
X
H
p-F
p-Cl
p-CH3
p-(i-Pr)
m-F
p-Cl
m-Br
m-CH3
�
0
0.06
407.6
2.841
0.23
409.8
3.159
� 0.17
409.2
2.378
� 0.15
410.4
1.816
0.34
405.8
3.426
0.37
407.8
3.551
0.39
409.0
3.713
� 0.07
406.0
2.642
Detected wavelength (nm)
kc � 10 (nm)
408.1
2.745
2
Note. [PhIO] = 5.26 � 10� mol � dm� 3. [[TPPFeIII]2O] = 1.5 � 10� 5 mol � dm� 3
3
.
III
[
TPPFe ]2O has an induction period of 3 h. In addition, the the same intermediate:
III
ability of [TPPFe ]2O to anti-PhIO is better than that of
III
PhIO + [TXPPFe ]2O
III
TPPFe Cl (12). The difference in catalytic power and the
III
stability, as well as the induction period of [TPPFe ]2O and
porphyrin oxidation
hydrocarbon hydroxylation.
III
→
[intermediate]
TPPFe Cl is possibly related to the antiferromagnetism
III
property of [TPPFe ]2O (8). Further studies will be car-
ried out.
The competing mechanism between cyclohexane oxida-
tion and the ring-splitting reaction of the porphyrin ring
in hydrocarbon hydroxylation in the [TXPPFe ]2O-PhIO
III
Preliminary Exploration on the Competing Mechanisms
between Cyclohexane Oxidation and the Ring Splitting
Reaction of the Porphyrin Ring in Hydrocarbon
system and the intermediate formed from PhIO and
III
[
TXPPFe ]2O will be studied further.
III
Hydroxylation in the [TXPPFe ]2O-PhIO System
ACKNOWLEDGMENT
It can be seen from Eqs. [3] and [4] that the signs of the
reaction constants are positive for cyclohexane oxidation
catalyzed by [TXPPFe ]2O with PhIO and the ring split-
This project was financially supported by The Chinese National Natural
Science Fund.
III
ting reaction of the porphyrin ring with PhIO, which shows
that the two reactions are promoted by electron-attracting
substitute groups on porphyrin rings. The fact that the two
reaction constants are 0.3186 and 0.3973 indicates that there
is little difference between the sensitivities of the reactions
to the electronic effect of substitute groups. The above facts
mean the two reactionspossiblyare competingreactionsvia
REFERENCES
1. Groves, J. T., Nemo, T. E., and Myers, R. S., J. Am. Chem. Soc. 104,
032 (1978).
1
2
3
. Meunier, B., Chem. Rev. 92, 1411 (1992), and references therein.
. Adler, A. D., Longo, F. R., Finarelli, J. D., Goldmacher, J., Assour, J.,
and Korsakoff, L. J., Org. Chem. 32, 476 (1967). [Guo, C.-C., He, X.-T.,
Zhou, G.-Y., and Youji Huaxue, 11, 416 (1991), CA 115:255864]
. Adler, A. D., Longo, F. R., Kampas, F., and Kim, J., J. Inorg. Nucl.
Chem. 32, 2443 (1970).
4
TABLE 7
5. Lucas, H. J., Kennedy, E. R., and Frormo, M. W., “Organic Syntheses,”
Coll. Vol. 3 (E. C. Horning, Ed.), p. 482. Wiley, New York, 1955.
Comparison of Cyclohexane Hydroxylation by [TPPFeIII]2O
6
7
8
9
. Fleischer, E. B., and Srivastava, T. S., J. Am. Chem. Soc. 91(9), 240
III
and TPPFe Cl
(
1969).
. Guo, C.-C., Gui, M.-D., Zhu, S.-J., and Huaxue Shiji, 12, 270 (1990),
CA 114:134975.
. Guo, C.-C., Zhu, S.-J., and Gui, M.-D., Acta Chim. Sin. 50, 129 (1992),
CA 116:206669.
Catalyst
Solvent
[TPPFeIII]2O
TPPFeIIICl
Cyclohexane Benzene Cyclohexane Benzene
. Zhu, S.-J., Gui, M.-D., Guo, C.-C., Chem. J. Chinese Univ. 10, 1100
Total yield (% )
Alcohol : ketone
62.60
3.64
35.80
5.70
43.87
4.50
24.55
7.10
(
1989), CA 112:186647.
1
1
0. Tsuchira, S., Seno, N., Chem. Lett. 206, 263 (1989).
1. Mansuy, D., Leclaire, J., and Fontecave, M., Biochem. Biophys. Res.
Commun. 119, 319 (1984).
2. Guo, C.-C., Zhang, S., and Lei, Y.-W., Acta Chim. Sin. 51, 928 (1993),
CA 120:63397.
(
mol ratio)
Time (h)
16
10
8
4
1
0
k � 10 (mol/min)
0.442
3
0.964
0
1.65
0
0.953
0
1
Induction period (h)