Structural effects on the NaOCl epoxidation of styrene in micellar media catalysed by amphiphilised Mn(III)metalloporphyrins

Article abstract of DOI:10.1016/S1381-1169(01)00406-X

A biomimetic system of cytochrome P450, constituted by [5-(4-(1-methylpyridinium))-10,15,20-triphenylporphyrinato] manganese(III) dichloride (Mn1) included in cetylpyridinium chloride (CPyCl) micellar phase, features good catalytic activity in the NaClO promoted epoxidation of styrene. A closely related system, i.e. [5-(4-(3-trimethylammonium) propyloxyphenyl)-10,15,20-tryphenyl-porphyrinato] manganese(III) dichloride (Mn2) in cetyltrimethylammonium bromide (CTAB), presents a lower reactivity, similar to that achieved in ethanol-water solvent mixture. A crossover experiment, i.e. that carried out with Mn1/CTAB system, shows intermediate degree of conversion. These findings indicate that the catalytic properties of the investigated systems are deeply influenced by the specific non-covalent interactions established among the catalyst, substrate, and surfactant.

Full text of DOI:10.1016/S1381-1169(01)00406-X

Journal of Molecular Catalysis A: Chemical 179 (2002) 125–131
Structural effects on the NaOCl epoxidation of styrene in micellar
media catalysed by amphiphilised Mn(III)metalloporphyrins
Donato Montia,∗, Alessandra Pastorinia, Giovanna Mancinib,1
,
Stefano Boroccib, Pietro Tagliatestaa
a
Dipartimento di Scienze e Tecnologie Chimiche, Università degli Studi di Roma “Tor Vergata”,
via della Ricerca Scientifica, I-00133 Rome, Italy
Dipartimento di Chimica, Centro C.N.R. di Studio sui Meccanismi di Reazione, Università degli
b
Studi di Roma “La Sapienza”, P.le Aldo Moro 5, 00185 Rome, Italy
Received 15 May 2001; received in revised form 24 August 2001; accepted 6 October 2001
Abstract
A biomimetic system of cytochrome P450, constituted by [5-(4-(1-methylpyridinium))-10,15,20-triphenylporphyrinato]
manganese(III) dichloride (Mn1) included in cetylpyridinium chloride (CPyCl) micellar phase, features good catalytic activity
in the NaClO promoted epoxidation of styrene.
A closely related system, i.e. [5-(4-(3-trimethylammonium) propyloxyphenyl)-10,15,20-tryphenyl-porphyrinato] man-
ganese(III) dichloride (Mn2) in cetyltrimethylammonium bromide (CTAB), presents a lower reactivity, similar to that achieved
in ethanol–water solvent mixture. A crossover experiment, i.e. that carried out with Mn1/CTAB system, shows intermediate
degree of conversion. These findings indicate that the catalytic properties of the investigated systems are deeply influenced
by the specific non-covalent interactions established among the catalyst, substrate, and surfactant. © 2002 Elsevier Science
B.V. All rights reserved.
Keywords: Catalysis; Epoxidation reaction; Micelles; Porphyrinoids; Selectivity
1. Introduction
porphyrin-based supramolecular architectures, featur-
ing cytochrome P450 biomimetic activity, [6–13] have
been realised and their catalytic features, in terms of
regioselectivity, shape-selectivity, as well as their ro-
bustness toward the degradative action of the oxidants,
make the systems investigated, though achievable by
demanding synthetic protocols, of great interest and
importance. The fact that P450 is a membrane-bound
enzyme sparkled the idea of building up a biomimetic
tool in which a synthetic heme core is included in
a self-organised medium. According to this philoso-
phy, properly tailored membrane-spanning porphyrins
[14–16], once embedded in a DMPC bilayer, are able
to catalyse the site-selective iodosylbenzene promoted
In the fervent arena of the porphyrin chemistry,
the development of a porphyrin-based system for
the selective oxidation of organic substrates [1–3]
represents one of the most challenging tasks de-
voted to the construction of synthetic systems able
to mimic the activity of metalloenzymes involved
in many life-sustaining cycles [4,5]. Intriguing
∗ Corresponding author. Tel.: +39-6-7259-4328;
fax: +39-6-7259-4738.
E-mail address: monti@stc.uniroma2.it (D. Monti).
1 Co-corresponding author.
1381-1169/02/$ – see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S1381-1169(01)00406-X

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D. Monti et al. / Journal of Molecular Catalysis A: Chemical 179 (2002) 125–131
epoxidation of steroid derivatives and of some fatty
acids. Other important results were reported by Nolte
and co-workers [17–19], who succeeded in the in-
corporation of all the features of natural cytochrome
P450 in liposome bilayer. Recently, a manganese(III)
porphyrin incorporated in polydimethylsiloxane syn-
thetic membranes has been reported to act as a selec-
tive catalyst for the epoxidation of deactivated allylic
alcohols [20].
Along this line, we reported [21] on a system
based on amphiphilised metalloporphyrins included
in micellar media, pointing out how the specificity
of the interactions between the macrocycles and
the surfactant aggregates strongly affects the cat-
alytic efficiency of these systems in the oxidation
of some probe olefins. Subsequently, we found that
the diastereoselective course of the epoxidation re-
action of chiral probe substrates can be influenced
by the microscopic aggregation of chiral surfactants
[22]. In the present paper, we wish to report on
the results obtained in the NaClO promoted epoxi-
dation of styrene and cyclooctene in micellar solu-
tion composed by cetylpyridinium chloride (CPyCl)
catalysed by [5-(4-(1-methylpyridinium))-10,15,20-
triphenyl-porphyrinato] manganese(III) dichloride
(Mn1, Scheme 1), in the presence of imidazole as
co-catalyst. The results obtained are compared to
those carried out in cethyltrimethylammonium bro-
mide micelle (CTAB), and in homogeneous con-
ditions (ethanol–water). The P450 activity of
[5-(4-(3-trimethylammonium)propyloxyphenyl)-10,
15,20-triphenyl porphyrinato] manganese(III) dichlo-
ride (Mn2) included in CTAB pseudo-phase was
also studied. The results obtained point out, once
more, the crucial role played by the microscopic in-
teraction between the substrate, catalyst, and micelle
aggregates on the efficiency of the catalytic systems
employed.
Scheme 1. Reaction scheme, porphyrin structures and idealised porphyrin-micelle catalytic system.

D. Monti et al. / Journal of Molecular Catalysis A: Chemical 179 (2002) 125–131
127
2. Experimental section
in 0.010 M aqueous CTAB or CPyCl (doubly distilled
water). The small fraction of the added organic solvent
(≤0.05%) safely does not alter the surfactant micro-
scopic organisation to a detectable extent. The resul-
tant solutions were incubated at 35 ◦C for 15 min and
the electronic spectra recorded. The relative spectro-
scopic features are reported in Table 1. Notably, the
clear solutions obtained were found to be stable in the
dark at room temperature and no significant alteration
(UV–visible check of the band intensities) or precipi-
tation was observed after several months of storage.
2.1. Instrumentation
GC analyses have been performed on a Carlo
Erba HRGC 5160 or on a Varian Vista equipped
with a Supelco SPB-35 capillary column. GC–MS
runs have been performed on a Varian 3400 matched
to a Mass Selective Detector Hewlett & Packard
HP-5970. UV–visible spectra were carried out on a
Perkin Elmer ␭ 18 Spectrophotometer equipped with
a thermostated cell holder. Mass spectra (FAB) were
recorded on a VG Quattro Triple Quadrupole Spec-
trometer using m-nitrobenzyl alcohol (NBA, Aldrich)
as a matrix in positive ion mode.
2.4. Synthesis
Porphyrin derivatives H21 and Mn2 have been
synthesised according to published procedures [25].
All the spectroscopic features are in agreement with
the reported data and confirm the identity of the
compounds. The Mn1 derivative has been prepared
by standard MnCl2/DMF metalation method from
free-base precursor H21 [26].
2.2. Materials
Reagents (Aldrich, Merck or Fluka) were of the
highest grade available and were used without fur-
ther purification. Solvents were dried, distilled and
degassed prior to use, by using standard procedures
[23]. Commercially available surfactants have been
purified according to literature methods [24]. Solvents
for UV–visible studies are of spectroscopic grade and
used as received.
2.5. Manganese [5-(4-(1-methylpyridinium))-10,15,
20-triphenyl-porphyrinato] dichloride (Mn1)
In a 50 ml round-bottomed flask, 56 mg (0.08 mmol)
of H21 and an excess of MnCl2·4H2O (25 mg,
0.13 mmol) were dissolved in 25 ml of carefully
degassed DMF. The reaction mixture was stirred
overnight at 80 ◦C under an inert atmosphere and
then left in the open air for 30 min. The solvent was
stripped off under reduced pressure and the solid dark
green residue dissolved in chloroform (50 ml). The
2.3. UV–visible spectroscopic studies
Porphyrin solutions for UV–visible studies of their
incorporation in micellar phases were prepared by
injection of the required amount of concentrated por-
phyrin stock solution (≈ 1 × 10−3 M, in 1,4-dioxane)
Table 1
Spectroscopic data of porphyrin catalysts Mn1 and Mn2 in various mediaa
Medium
λmax, nm (Log ε)
Mn1
Mn2
CHCl3
CPyCl
CPyClb
EtOH/H2Oc
378 (4.6), 406 (4.3), 424 (4.1), 480 (4.8), 583 (3.9), 621 (3.8)
382 (4.5), 403 (4.4), 424 (4.3), 470 (4.9), 564 (3.9), 600 (3.5)
380 (4.4), 406 (4.3), 427 (4.0), 472 (5.0), 584 (3.8), 622 (3.6)
376 (4.3), 398 (4.4), 420 (4.3), 468 (5.0), 568 (3.8), 602 (3.6)
CHCl3
378 (4.6), 403 (4.6), 425 (4.4), 478 (5.0), 583 (3.9), 620 (4.1)
383 (4.6), 403 (4.5), 425 (4.4), 472 (4.9), 573 (3.8), 606 (3.5)
381 (4.5), 406 (4.5), 425 (4.2), 472 (4.9), 586 (3.6), 624 (3.4)
379 (4.5), 400 (4.7), 420 (4.3), 467 (5.0), 567 (4.0), 601 (3.5)
CTAB
CTABb
EtOH/H2Oc
a [Surfactant] = 0.01 M; T = 25 ◦C.
b In the presence of imidazole, 5 × 10−3 M.
c EtOH/H2O (80:20, v/v) solvent mixture.

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D. Monti et al. / Journal of Molecular Catalysis A: Chemical 179 (2002) 125–131
resulting solution was filtered from the solid residues
constituted by the excess of metal salts and washed
with a 5% HCl aqueous solution (50 ml), then with
brine until neutrality. The organic phase was dried
(Na2SO4) and the solvent removed under reduced
pressure. The residue, constituted by virtually pure
Mn1, was recrystallised from CH2Cl2/hexane to give
50 mg (0.06 mmol, 82% yield) of the title porphyrin
derivative as a green microcrystalline powder.
the appropriate molar ratios as above described. The
reaction mixture was then extract (petroleum ether)
and analysed (GC and GC–MS).
3. Results
3.1. UV–visible spectroscopic studies
UV–visible spectroscopic studies on the porphyrin
derivatives Mn1 and Mn2 were carried out in order
to investigate the behaviour of such species in mixed
aqueous solvent and micellar solutions. Ethanol/water
(8:2, v/v) solvent mixture was safely taken as refer-
ence solvents for CTAB and CPyCl micellar phases
[28]. The porphyrin derivatives were soluble in chlo-
rinated solvents, ethanol, or 1,4-dioxane. The incor-
poration of porphyrin derivatives in micellar phases
(0.01 M) has been accomplished by the injection
method (see Section 2), from the relative 1,4-dioxane
concentrated stock solutions (Fig. 1). The inclu-
sion in micellar phases results in a peculiar shift of
the absorption maxima (Table 1). In particular the
LMCT band [29], at about 480 nm in chloroform, is
blue-shifted by 7–10 nm in micellar phase, toward
the values observed in EtOH/water solution. The in-
clusion of porphyrin derivatives Mn1 and Mn2 in
the micellar phases has been found to be complete
even at values of porphyrin/surfactants ratio as high
as 0.05, in CPyCl and CTAB respectively, without
the occurrence of a detectable degree of aggregation
(UV–visible). This is indicated by the excellent degree
of linearity of the relative Lambert–Beer curve (e.g.
porphyrin LMCT or Soret band), within the examined
concentration window, well above 5 × 10−4 M. These
concentration ratios are consistently used in the epox-
idation experiments (vide infra). The coordination of
imidazole to the micelle-included metalloporphyrin
is witnessed by the typical red shift of the LMCT
band (Table 1). The role of the added ligand is to
mimic the cysteine axial ligand of P450 in vivo en-
zyme [5]. Notably, the simple addition of imidazole
to Mn1 or Mn2 included in micelle hardly results
in the axially coordinated species, owing to the low
degree of binding of the nitrogen base to the micelle
pseudo-phase. The axial ligation is then effectively
achieved by co-solubilisation of the species prior to
surfactant addition (see Section 2).
UV–visible(CHCl3); λmax
:
378, 406, 424, 480, 583, 621 nm
FAB-MS(NBA); m/e: 683[M + H − 2Cl]+,
668[M − 2Cl − CH3]+
2.6. Epoxidation reactions
The solutions for the epoxidation experiments,
containing surfactant, catalyst, imidazole, oxidant,
and substrate in a 1/0.05/1/10/0.5 molar ratio, were
prepared as follows. In a 3 ml vial equipped with
a magnetic stirring apparatus, the required amount
of porphyrin catalysts (1Mn or 2Mn) and imidazole
were co-dissolved in 400 ␮l of dichloromethane. The
resulting solution is briefly sonicated to homogeneity
and the solvent removed by gentle warming with the
aid of an argon stream. The appropriate surfactant so-
lution (2 ml, 0.01 M) containing the required amount
of olefin was then added, and the resulting mixture
stirred to homogeneity. The reaction mixture was
incubated at 35 ◦C for 15 min, then cooled to 25 ◦C.
Aliquots of the oxidant solution, e.g. buffered (solid
NaHCO3, pH ca. 10) NaClO [27], were added and the
resulting mixture vigorously stirred for 10 min. An
internal standard (n-decane or n-dodecane) was then
added and an aliquot (200 ␮l) of the reaction mixture
was taken, quenched with methanol (100 ␮l) to disrupt
the micellar aggregates, filtered from the eventually
precipitated salts and extracted with petroleum ether.
The organic phase was analysed by GC and GC–MS.
Runs were triplicate and were reproducible within
5%. The reaction products have been characterised
by comparisons (GC and GC–MS) with authentic
samples. As far as the reactions in EtOH/H2O solvent
mixture are concerned, the oxidant was added to a
2 ml solution of catalyst, imidazole and olefin, held in

D. Monti et al. / Journal of Molecular Catalysis A: Chemical 179 (2002) 125–131
129
Fig. 1. UV–visible spectra of Mn1 (1 × 10−5 M) in (a) CPyCl, 0.01 M and (b) CHCl3.
3.2. Reactivity studies
chlorohydrine were detected. Conversely, the reaction
carried out on cyclooctene gave only moderate yield
of epoxide product. Blank experiments, carried out in
the absence of catalyst, yielded chlorohydrine, as ma-
jor products, and small amounts of other not identified
products. The reactions carried out in the reference
ethanol/water solvent mixture yielded a substantially
Epoxidation reactions of olefins by using NaOCl as
oxygen atom donor were carried out at 25 ◦C in micel-
lar aggregates formed by CPyCl or CTAB surfactants
in the presence of catalytic amounts of Mn1 or Mn2,
respectively, and an excess of imidazole as co-catalyst.
The choice of the surfactant was made on the bases
of previous results [21,22], showing that the optimal
performance of a catalytic system is achieved when
the porphyrin and the surfactant were characterised by
polar heads of like structure.
Table 2
NaOCl promoted epoxidation reaction of styrene in various aque-
ous mediaa
Yield (%)b
The concentration of the surfactants was fixed at
1×10−2 M, a value at least 1 order of magnitude above
the cmc (9.0 ×10−4 and 8.0 ×10−4 M for CPyCl and
CTAB, respectively), in order to safely exclude any
contribution of the surfactant monomeric form [30].
The concentration of the catalyst was consequently
held at 5.0×10−4 M, so that a minimum average value
of two molecules of porphyrin per micelle can be es-
timated, being the aggregation number of CPyCl and
CTAB about 90 and 60, respectively [31,32]. This en-
sures both the complete incorporation of the catalysts
in the micellar phase, and a high probability of the pro-
ductive encounter event between the reactants and the
catalyst. The reactions were stopped at a fixed time,
10 min, and analysed by GC and GC–MS (see Sec-
tion 2). As far as the Mn1/CpyCl system is concerned,
styrene was smoothly converted to the epoxide, and
only traces of ring opening derivatives (1,2-diols) or
Entry
Catalyst
Medium
1
Mn1
Mn1
Mn1
Mn1
None
Mn2
Mn2
Mn2
CPyCl
CPyCl
CTAB
EtOH/H2Od
CPyCl
CTAB
EtOH/H2Oc
CTAB
90
10
25
2c
3
4
5
6
7
8f
25
e
20
23
8
a [catalyst] = 5.0×10−4 M, [imidazole] = 0.01 M, [NaOCl] =
0.10 M, [surfactant] = 0.01 M, [olefin] = 5.0 × 10−3 M, T =
25 ◦C.
b Product yields are based on starting olefin and referred to a
reaction time of 10 min. Errors lie within 5% range.
c Epoxidation reaction of cyclooctene, in the above reaction
conditions.
d EtOH/H2O 80:20 (v/v) solvent mixture.
e Epoxide formation was not detected. A 35% chlorohydrine
was formed.
f Epoxidation reaction of cyclooctene (see [21,22]).

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D. Monti et al. / Journal of Molecular Catalysis A: Chemical 179 (2002) 125–131
lower degree of substrate conversion. It is worth of
noting that, in this latter case, an evident extent of cat-
alyst bleaching is found on increasing the amount of
NaClO. In the case of the reaction carried out with the
Mn2/CTAB system a lower degree of substrate con-
version, similar to that achieved by performing the re-
action in aqueous ethanol is observed. A comparative
run of Mn1 in CTAB has been made, to give a mod-
erate conversion to styrene epoxide. The results have
been summarised in Table 2.
cyclooctene, are converted to their relative epoxides
only to a moderate extent. This can be explained in
terms of the nestling of the catalysts in a pocket of
the micelle hardly accessible to these substrates, mak-
ing the probability of their productive encounter event
substantially low.
This interpretation does not hold, however, for the
higher reactivity observed for Mn1 in CPyCl toward
styrene. Different factors, such as the occurrence of
specific cation–␲ interaction [38] between the CPyCl
polar head group and the aromatic ring of the sub-
strate, would come into play. These non-covalent in-
teractions are known to play a fundamental role in
supramolecular host–guest recognition [39] as well as
in important biological systems [40,41]. In our case,
these hydrophobic forces may steer the course of the
reaction driving the reactants in a mutual close prox-
imity, being the Mn1 catalyst reasonably located in
the surfacial region of the micelle aggregates.
4. Discussion
The Mn1/CpyCl system shows enhanced catalytic
activity in the NaOCl promoted oxidation of styrene,
compared to that observed in homogeneous condition.
High styrene conversion is usually achieved, in fact,
in the presence of more elaborate porphyrin deriva-
tives such as, e.g. polyhalogenated [33] or sterically
hindered [34] macrocycles. Moreover, the increased
stability of the catalyst underlines the beneficial ef-
fect exerted by the surfactant microenvironment. The
comparison to Mn2/CTAB counterpart to crossover
Mn1/CTAB system should shed some light on the cru-
cial role which is played by the non-covalent inter-
actions established among the substrate, the catalyst
and the organised media, on the features of the reac-
tion. The different reactivity featured by the catalysts
should not be attributed to the occurrence of aggrega-
tion phenomena, being the porphyrins included in the
respective micellar phase in the monomeric form. It is
known that the location of the catalysts within micel-
lar phases can be modulated by the different nature of
the appended groups that characterise the porphyrin
frames [25,35,36]. In the case of Mn1 and Mn2, the
presence of a positive charge on the periphery of both
of the macrocycles should drive their location in a re-
gion of the aggregates close to the water–micelle in-
terface. This is witnessed by the similarity of their
spectroscopic features in EtOH/water and surfactant
media (Table 1) and by their similar reactivity toward
lipophilic substrates, once included in cationic CTAB
micelle (Table 2). In this surfactant solution, in fact,
hydrophobic substrates [21,22] 2 , such as styrene and
5. Conclusions
A biomimetic system of cytochrome P450, consti-
tuted by a metalloporphyrin included in a micellar
phase, has been described and the properties of the
resulting assemblies, in terms of catalytic activity to-
ward the epoxidation of styrene, have been studied.
The results obtained point out the fundamental role of
the affinity of the tetrapyrrolic macrocycles and the
substrate toward the micellar phases. Further studies,
aimed at the construction of a biomimetic catalyst with
tuneable stereoselective properties, are currently un-
der investigation in our laboratories.
Acknowledgements
The authors are deeply indebted with Mr. Alessan-
dro Leoni and Mr. Giuseppe D’Arcangelo for their
valuable technical help. Moreover, we thank the refer-
ees for their useful comments. The financial supports
of Ministero dell’Università e della Ricerca Scientifica
e Tecnologica (MURST Project No. 98032774402—
strate between n-buthanol and water. Log P: cyclooctene = 2.91;
styrene = 2.70. Calculation of log P are carried out according to
Viswanadan et al. [37].
2 The hydrophobicity of a given substrate can be quantified by
the “log P” value, where P is the partition constants of the sub-

D. Monti et al. / Journal of Molecular Catalysis A: Chemical 179 (2002) 125–131
131
Progetti di Ricerca Scientifica di Rilevante Interesse
Nazionale) is gratefully acknowledged.
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