734 J. Phys. Chem.

B 2000, 104, 734-740

Direct Methane-Methanol and Benzene-Phenol Conversions on Fe-ZSM-5 Zeolite:

Theoretical Predictions on the Reaction Pathways and Energetics

Kazunari Yoshizawa,* Yoshihito Shiota, Takashi Yumura, and Tokio Yamabe

Department of Molecular Engineering, Kyoto UniVersity, Sakyo-ku, Kyoto 606-8501, Japan, and Institute for
Fundamental Chemistry, 34-4 Takano-Nishihiraki-cho, Sakyo-ku, Kyoto 606-8103, Japan
ReceiVed: June 7, 1999; In Final Form: NoVember 20, 1999

The reaction pathways and the energetics for the direct methane-methanol and benzene-phenol conversions
that occur on the surface of Fe-ZSM-5 zeolite are analyzed from B3LYP DFT computations. We propose
a reasonable model for “R-oxygen”, a surface oxygen species responsible for the catalytic reactivities of
Fe-ZSM-5 zeolite. Our model involves an iron-oxo species on the AlO4 surface site of the zeolite as a
catalytic active center and as a source of oxygen. The essential features of the reaction pathways for the
methane-methanol and benzene-phenol conversions are identical, especially in bonding characters. In the
initial stages of each reaction, methane or benzene comes into contact with the active iron site of the “R-
oxygen” model, leading to the reactant (methane or benzene) complex. After the initial complex is formed,
each reaction takes place in a two-step concerted manner, via neither radical species nor ionic intermediates.
The concerted reaction pathway for the methane (benzene) hydroxylation involves an H atom abstraction and
a methyl (phenyl) migration at the iron active center. From computed energetics for the reaction pathways,
we predict that the benzene hydroxylation should be energetically more favorable than the methane
hydroxylation.

Introduction al.4 showed that methanol is produced at room temperature from

ZSM-5 zeolite exhibits an extremely high catalytic selectivity
for the oxidation of benzene to phenol. Panov and collaborators1
have suggested that the high reactivity of the zeolite should be
ascribed to impurity iron, which is added mainly along with
the starting ingredients at the step of zeolite synthesis. Samples
of ZSM-5 containing 0.07-0.72 wt % of iron calculated for
Fe2O3 demonstrated excellent results; the selectivity for phenol
was reported to be 100% at 20-25% conversion levels of
benzene over Fe-ZSM-5 zeolite at 300-400 °C. A surface
oxygen species generated on Fe-ZSM-5 zeolite under N2O
decomposition, as indicated by (O) in reaction 1, has been
N2O + ( ) f (O) + N2 (1)
(O) + C6H6 f C6H5OH (2)
proposed to be responsible for the formation of phenol from
benzene (reaction 2); such an oxygen species is called “R-
oxygen” by Panov et al.1 According to ref 2, Solutia recently
developed a one-step technology that produces phenol directly
from benzene and N2O. Since this process provides a very high
yield and can use waste N2O from the production of adipic acid,2
it is considered to be a hopeful technology in the coming next
century.
The conversion of methane to methanol has been reported to
also take place over Fe-ZSM-5 zeolite using N2O as a source
of oxygen. Anderson and Tsai3 reported from high-temperature
experiments that the conversion rate of methane is very low
and that the products include CO2, CO, and HCHO as
byproducts in high concentrations. On the other hand, Panov et
* To whom all correspondence should be addressed at Kyoto University.
E-mail: kazunari@scl.kyoto-u.ac.jp.
10.1021/jp991844b CCC: $19.00 © 2000 American Chemical Society
Published on Web 01/05/2000
a single-turnover run in high yield (80 %), suggesting that the
product methanol that is strongly bound to the surface of zeolite
can be extracted by using a mixture of water and acetonitrile.
As indicated in reaction 3, “R-oxygen” has been also proposed
(O) + CH4 f CH3OH (3)
to be responsible for this intriguing catalytic reactivity of the
zeolite toward methane. It seems to us that the methane-
methanol process is difficult compared to the benzene-phenol
process, judging from the limited number of papers published
concerning the methane hydroxylation. Once methanol is
produced, the further oxidation of methanol into formaldehyde,
formic acid, or carbon oxides can take place more easily than
the oxidation from methane to methanol. Thus, it may be
difficult to control the further oxidation of methanol over Fe-
ZSM-5 zeolite.
Schröder and Schwarz5-7 showed that the bare FeO+ complex
reacts with methane and benzene in the gas phase, yielding
methanol and phenol, respectively, in high yield. Interestingly,
the FeO+ species is also generated in the gas phase from the
reaction of Fe+ with nitrous oxide. Thus, an analysis of the
interesting gas-phase reactions is the key to understanding the
catalytic hydroxylations of methane and benzene over Fe-
ZSM-5 zeolite. Shaik et al.8 have proposed that more than one
state should be involved in the reactions catalyzed by organo-
metallic systems in remarkable contrast to organic reactions in
which one state plays a dominant role; they call such a
phenomenon “two-state reactivity”.
From density-functional-theory (DFT) computations, we have
proposed that the direct methane-methanol conversion by FeO+
should take place in the following manner: FeO+ + CH4 f
OFe+(CH4) f [TS1] f HO-Fe+-CH3 f [TS2] f Fe+(CH3-
Methane-Methanol and Benzene-Phenol Conversions
OH) f Fe+ + CH3OH, in which TS stands for transition state.9
The proposed reaction pathway involves the reactant complex,
the hydroxy intermediate, the product complex, and the two
transition states (TS1 and TS2). We call this mechanism the
“two-step concerted mechanism”. The potential energy surface
of the quartet state lies below that of the sextet state in the
middle of the reaction pathway, and therefore the quartet
potential energy surface plays an essential role in this direct
methane hydroxylation. In a recent paper,10 we theoretically
demonstrated that the gas-phase benzene-phenol conversion
by FeO+ should take place in an identical manner with respect
to essential bonding characters: FeO+ + C6H6 f OFe+(C6H6)
f [TS1] f HO-Fe+-C6H5 f [TS2] f Fe+(C6H5OH) f Fe+
+ C6H5OH.
Taking cognizance of the experimental results mentioned
above and our previous theoretical analyses,9,10 we set up a
working hypothesis that “R-oxygen” should have relevance to
an iron-oxo species supported on the surface of Fe-ZSM-5
zeolite and we proposed how such a reactive oxygen species is
generated upon decomposition of N2O.11 Our hypothesis is
reasonable if a coordinatively unsaturated iron-oxo species is
responsible for the C-H bond activation of methane, benzene,
and other hydrocarbons. In this article, we address how the
hydroxylations of methane and of benzene take place on the
surface of Fe-ZSM-5 zeolite using a possible cluster that can
model “R-oxygen”. The reaction species and the energetics along
the reaction pathways are analyzed in detail from DFT
computations. It is useful to investigate the interesting catalytic
functions of the zeolite from the viewpoint of quantum chemical
calculations because of possible implications for the rational
design of high-performance catalysts.
Method of Calculation
We optimized local minima and saddle points on potential
energy surfaces using the hybrid Hartree-Fock/density-functional-
theory (HF/DFT) B3LYP method.12,13 This method consists of
the Slater exchange, the Hartree-Fock exchange, the exchange
functional of Becke,12 the correlation functional of Lee, Yang,
and Parr (LYP),13 and the correlation functional of Vosco, Wilk,
and Nusair.14 The hybrid B3LYP method has been reported to
provide excellent descriptions of various reaction profiles,
particularly in geometries, heats of reaction, barrier heights, and
vibrational analyses.15 As indicated in a previous paper,10 the
B3LYP method correctly reproduces an experimental dissocia-
tion energy of FeO+ (81.4 ( 1.4 kcal/mol).16 The method of
choice is therefore appropriate for the present study. For the Fe
atom we used the (14s9p5d) primitive set of Wachters,17 and
for the H, C, O, Al, and Si atoms we used the 6-31G** basis
set,18 a standard double-ζ basis set with polarization functions.
The sextet and quartet spin states were considered for the
methane hydroxylation and only the quartet state was considered
for the benzene hydroxylation. The spin-unrestricted method
was applied to such open-shell systems. Computed 〈S2〉 values
confirmed that the spin contamination included in calculations
was very small (within 0.3% after annihilation of spin contami-
nation). Vibrational analyses were systematically performed for
all transition states to confirm that they have only one imaginary
mode of vibration and for all reaction intermediates along the
methane-methanol conversion pathway. The Gaussian 94
program package19 was used in this study.
A Possible Model of “r-Oxygen”
Before discussing the reaction pathways for the hydroxyla-
tions of methane and benzene on Fe-ZSM-5 zeolite, let us first
J. Phys. Chem. B, Vol. 104, No. 4, 2000 735
CHART 1
set up a reasonable model of “R-oxygen”. To the best of our
knowledge, there is no detailed structural information on
transition metals supported on zeolite, particularly concerning
whether such metal active centers are isolated or coupled.
Kucherov and Slinkin20 proposed from ESR measurements that
supported Cu, Cr, and Fe cations should be located in nonlattice
(surface) positions of ZSM-5 zeolite. Analyses on the active
center of Cu-ZSM-5 zeolite,21,22 which exhibits an important
catalytic function of NOx decomposition,23 have been carried
out using reasonable zeolite models. From semiempirical
quantum-chemical calculations using dinuclear model com-
plexes, Filatov et al.24 showed that N2O decomposition does
not occur at an Al atomic center but occurs at an Fe atomic
center of zeolite, suggesting that “R-oxygen” should derive from
an impurity iron supported on ZSM-5 zeolite. Taking the general
features of zeolite into account,25 we set up our model complex
(Chart 1), in which an iron-oxo species is located on the AlO4
surface site as a catalytic active center and as a source of oxygen.
In a previous paper,11 we presented from B3LYP calculations
how such a reactive surface species is generated upon decom-
position of nitrous oxide (N2O) on the surface of Fe-ZSM-5
zeolite and proposed the possible form of “R-oxygen”. The
activation energy for the decomposition of N2O was computed
to be 2.4 kcal/mol and the entire reaction 63.5 kcal/mol
exothermic; we thus expect the decomposition of N2O to readily
occur on the active site of Fe-ZSM-5 zeolite. The iron active
center is three-coordinate in this model, but four- or even five-
coordinate iron is also possible in that the metal active center
is coordinatively unsaturated. From the viewpoint of known
catalytic chemistry, it is in general reasonable to assume that
catalytically active metal complexes might be coordinatively
unsaturated. If such an iron-oxo species is generated on the
surface of the zeolite, it should become a reaction center that
affords a coordination site for methane, benzene, and other
hydrocarbon molecules. The oxo species is, of course, a source
of oxygen in the oxidation of these hydrocarbons. Since the Fe
atom is +3 in formal charge, the oxo species -2, the Al atom
+3, the OSiH3 group -1, and the OH group -1, the total charge
of the model complex is counted as neutral. We considered the
sextet and quartet spin states for our computational analyses
because of the detailed analyses of the gas-phase reactions by
the bare FeO+ complex9,10 discussed above. A computed
structure of our model of “R-oxygen” in the quartet state is
shown in Chart 1, in which bond distances indicated are in
angstroms and bond angles (italic) are in degrees. Atomic
charges and spin densities in the sextet and quartet states are
listed in Table 1. Computed spin densities reside mainly on the
iron-oxo moiety, as expected. In the following section, we will
look in detail at the reactions of methane and benzene on “R-
oxygen” of Fe-ZSM-5 zeolite using this simple, but rather
reasonable model.
736 J. Phys. Chem. B, Vol. 104, No. 4, 2000
TABLE 1: Computed Atomic Charges and Spin Densities
on a Model of “r-oxygen” of Fe-ZSM-5 Zeolite
quartet sextet
atom atomic charge spin density atomic charge spin density
Fe +1.30 +3.15 +1.38 +3.97
O(oxo) -0.63 -0.22 -0.67 +0.93
O -0.85 +0.03 -0.86 +0.05
Si +0.40 +0.01 +0.39 +0.01
Al +0.91 -0.01 +0.91 -0.01
Methane Hydroxylation on Fe-ZSM-5 Zeolite
Structures of the Reaction Species. Having set up our model
of “R-oxygen”, let us next consider the methane hydroxylation
on it. In this section we look at computed geometries of the
reaction species in the quartet spin state for the conversion of
methane to methanol on the model complex. The reaction
pathway that we address here is essentially identical to that of
the gas-phase methane-methanol conversion by FeO+.9 Since
the low-spin quartet potential energy surface provides a low-
cost energy pathway, as described later, we take a look at the
reaction species on the quartet reaction pathway. Optimized
structures of the reaction species in the sextet state are similar
to those in the quartet state. The first step of this reaction is
C-H bond activation of methane. As shown in Figure 1, a
methane (or reactant) complex is formed in the initial stages of
the reaction. The methane molecule is weakly bound to the
three-coordinate iron of the model complex; computed binding
energies of 1.6 and 3.9 kcal/mol in the quartet and sextet states,
respectively, are small, but we think that the formation of this
complex is very much indicative of methane activation. We
predict from DFT computations that the Fe ion is closer to one
pair of H atoms of the bound methane; this initially formed
species is an η2-CH4 complex. Since methane is bound to the
neutral complex, the driving force for this binding is unlikely
to be direct electrostatic interactions between the methane
molecule and the complex. Methane complexes with an η2- or
η3-CH4 binding mode have been proposed to be involved in its
C-H bond activation; extensive indirect data have been obtained
to support the intermediary of small-alkane complexes.26 One
such example was obtained by Billups et al.26i The neutral Co-
(CH4) complex is formed during photolysis of the CH3CoH
complex in an argon matrix, which was confirmed from the
observation that the triply degenerate T2 vibrational mode of
methane at 1305 cm-1 was observed from FTIR measurements
to split into two peaks in the Co(CH4) complex.
After this methane complex is formed, one of the H atoms
of the methane molecule is abstracted in a concerted fashion
via a four-centered transition state (TS1), leading to a reaction
intermediate that involves the resultant OH and CH3 groups as
ligands. We call this species a hydroxy intermediate, which plays
a central role in the methane-methanol conversion. This process
can be viewed as a [1,3] migration of the H atom; the
dissociating C-H bond and the forming O-H bond were
predicted to be 1.309 and 1.357 Å, respectively, the values being
appropriate for this concerted electronic process. This four-
centered structure is quite similar to the corresponding transition-
state structure in the gas-phase process by the bare FeO+
complex. This mechanism for the C-H dissociation of hydro-
carbon substrates is strikingly different from the conventional
radical mechanism that is considered to take place through a
transition state with a linear C-H-O array.
The second half of the reaction starts from the hydroxy
intermediate. The hydroxy intermediate thus formed is then
converted into a methanol (or product) complex in a concerted
Yoshizawa et al.
manner via a three-centered transition state (TS2) in which an
Fe-C bond breaking and a C-O bond formation occur
simultaneously, as indicated in Figure 1. This transition state
correctly connects the hydroxy intermediate and the product
complex, being responsible for an intramolecular [1,2] methyl
migration. Optimized Fe-C and O-C distances are 2.543 and
1.852 Å, respectively. The three-centered structure of TS2 is
thus appropriate for the transition state of the concerted methyl
migration from the Fe ion to the OH group.
Let us finally look at the product complex that involves
methanol as a ligand. The basic structure of the methanol moiety
in the product complex is not significantly changed from that
of free methanol. The Fe-O distance of 1.989 Å is much longer
than 1.608 Å in the reactant complex and 1.765 Å in the hydroxy
intermediate. The Fe-O bond of the product complex is thus
viewed as a typical coordinate bond in contrast to those of the
reactant complex and the hydroxy intermediate. The product
complex and the final complex from which methanol is released
involve Fe(I) that needs to be reoxidized back to Fe(III) upon
decomposition of N2O. In a previous paper,11 we studied from
DFT computations the energetics for the conversion of [Fe]+
f [FeO]+ by N2O that regenerates the active center for further
reaction. Fe(I) is in general a rather unstable oxidation state for
iron, but according to a textbook,27 the existence of Fe(I) cannot
be ruled out. Panov et al.4b proposed a diiron model that
reasonably allows two-electron oxidation-reduction between
Fe(III)/Fe(III) and Fe(II)/Fe(II). Our mechanism is, of course,
extended to diiron complexes, as can be seen in our previous
papers on the mechanism of methane monooxygenase.28
We have described the essential electronic processes for the
methane hydroxylation on a model of “R-oxygen”. The most
important point of our proposal for the reaction pathway is that
methane is activated on a coordinatively unsaturated iron-oxo
species leading to a methane complex and that two-step
concerted migrations of hydrogen and methyl successfully
convert methane to methanol on the complex. Finally, we should
indicate that the structure of the four-sided figure of FeO2Al
remains almost unchanged throughout the reaction and that the
catalytically active center can be reproduced by the introduction
of N2O gas.
Energetics for the Hydroxylation of Methane. We present
in Figure 2 computed energy diagrams in the sextet and quartet
spin states for the methane hydroxylation on the possible model
of “R-oxygen” of Fe-ZSM-5 zeolite. The overall reaction is
23.9 kcal/mol endothermic on the quartet surface and 26.0 kcal/
mol endothermic on the sextet surface. The essential features
of the energy diagrams are similar to those of the gas-phase
process by FeO+.9 We see crossing between the two potential
energy diagrams to occur twice in the vicinity of the reactant
and the product complexes. Spin inversion can take place in
the vicinity of these crossing points. From an inspection of the
two energy diagrams, we expect that the quartet potential surface
should afford an energetically low-cost reaction pathway
whereas the sextet state is the ground state in the entrance and
the exit channels. Although the crossing occurs twice near the
reactant and the product complexes, the spin inversion has little
effect on the energetics of the reaction pathway because the
sextet and the quartet states in the entrance and the exit channels
are close-lying in energy. We therefore conclude that the quartet
potential energy surface should play a dominant role in this
reaction, which is somewhat different from that of the reaction
pathway for the gas-phase methane-methanol conversion by
FeO+,9 where such spin inversions play a very important role
in determining the energetics of the reaction pathway.8a
Methane-Methanol and Benzene-Phenol Conversions
Figure 1. Ball-and-stick structures of the reaction intermediates and the transition states for the direct methane hydroxylation on a model of
“R-oxygen” of Fe-ZSM-5 zeolite in the quartet state. Bond lengths are in angstroms.
Figure 2. Potential energy diagrams for the direct methane hydroxy-
lation on a model of “R-oxygen” of Fe-ZSM-5 zeolite in the sextet
and the quartet states. Note that the reaction proceeds in a two-step
manner, via TS1 and TS2. Relative energies, which include zero-point
energy corrections, are in kcal/mol. SI means spin inversion.
Let us look in detail at the energetics of the catalytic methane
hydroxylation on the model complex. As mentioned above, we
can draw general conclusions on the energetics in view of the
quartet potential energy surface. The methane molecule is bound
to the three-coordinate iron of the model complex with a small
binding energy of 1.6 kcal/mol. The activation barrier for the
C-H bond cleavage via TS1 was predicted to be 11.4 kcal/
mol if measured from the reactant complex and 9.8 kcal/mol
J. Phys. Chem. B, Vol. 104, No. 4, 2000 737
from the dissociation limit on the quartet potential energy
surface. These values are small compared to the C-H dissocia-
tion energy of methane (104 kcal/mol). It is interesting to
compare the activation energy for the catalytic H atom abstrac-
tion on the “R-oxygen” model with those in the gas-phase
process by the bare FeO+ complex.9 In the gas-phase process,
the corresponding barrier height for TS1 was computed to be
15.7 kcal/mol from the reactant complex and 6.5 kcal/mol from
the dissociation limit on the quartet potential energy surface.9b
Thus, the energetics for the C-H bond cleavage of methane is
comparable in both processes because of the similar four-
centered structures of TS1. The resultant hydroxy intermediate
is extremely stable in energy in both spin multiplicities.
Therefore, this intermediate might be detected at low temper-
ature using modern spectroscopic techniques.
The barrier height for TS2 was predicted to be 41.6 kcal/
mol on the quartet potential energy surface if measured from
the hydroxy intermediate, which is extremely stable in energy.
Therefore, once the hydroxy intermediate is formed, it seems
to us that this activation energy would require very high
temperatures for the reaction to be facile. This view is correct
if we confine our discussions to the chemical reactions on the
computed adiabatic potential. However, we think that either
kinetic energy that the reaction system possesses or energy
transfer from the external field can overcome this activation
barrier. In fact, if we measure the activation barrier for TS2
from the dissociation limit, it becomes 13.2 kcal/mol. Consider-
ing this potential energy profile of the reaction system, this
electronic process can be thermally accessible. If the reaction
system preferentially moves on the quartet potential energy
738 J. Phys. Chem. B, Vol. 104, No. 4, 2000
Figure 3. Ball-and-stick structures of the reaction intermediates and the transition states for the direct benzene hydroxylation on a model of
“R-oxygen” of Fe-ZSM-5 zeolite. Bond lengths are in angstroms.
surface, 26.6 kcal/mol is required for the release of the product
methanol. Even if we consider the spin inversion to take place
in the exit channel, this value would not change because the
sextet and the quartet states of the product complex, indicated
at right in Figure 2, are close-lying in energy. Thus, the quartet
potential energy surface plays a dominant role in this reaction.
Benzene Hydroxylation on Fe-ZSM-5 Zeolite
Structures of the Reaction Species. Economical, direct
conversion of benzene to phenol over Fe-ZSM-5 zeolite has
attracted the attention of researchers in applied chemistry,2 but
little is known of the reaction mechanism by which benzene is
oxidized to phenol. We believe that our theoretical study on
the benzene hydroxylation on Fe-ZSM-5 zeolite will be of
significant use in the interpretation of the catalytic processes
and in the rational design of high-performance zeolite catalysts.
In a previous paper,10 we addressed the reaction pathway and
the energetics for the gas-phase benzene-phenol conversion
by the bare FeO+ complex. We can apply our previous results
to the catalytic processes on Fe-ZSM-5 zeolite.
Figure 3 presents ball-and-stick structures for the reaction
intermediates and the transition states along the reaction pathway
for the benzene hydroxylation on the “R-oxygen” model. The
reaction mechanism is identical to that for the methane
hydroxylation discussed earlier in essential bonding characters.
Our discussions can be reasonably restricted to the reaction
pathway in the quartet state because the quartet potential energy
surface is low-lying compared to the sextet state and thus the
Yoshizawa et al.
reaction system should move preferentially on the quartet
potential energy surface judging from the previous study on
the corresponding gas-phase process.10 The initially formed
complex exhibits an η2-C6H6 mode in which the Fe ion is closer
to one pair of carbon atoms of the benzene ring. The benzene
ring remains nearly planar, so the complex is a kind of π
complex. The binding energy for the reactant complex was
predicted to be 10.2 kcal/mol. After this complex is formed, an
H atom abstraction occurs via TS1 that connects the reactant
complex and the hydroxy intermediate. The C-H bond and the
O-H bond in the four-centered structure were computed to be
1.298 and 1.364 Å, respectively. These values are reasonable
for a transition-state structure responsible for C-H bond
breaking and O-H bond forming. The C-H bond is signifi-
cantly deviated from the benzene plane, and the four-centered
structure is nearly orthogonal to the benzene plane. Thus, the
first half of the reaction ends with the formation of the
intermediate complex that involves the resultant OH and C6H5
groups as ligands.
We next take a look at the hydroxy intermediate. This
intermediate is likely to play a central role in the reaction
pathway for the benzene-phenol conversion, by analogy with
the reaction pathway for the methane-methanol conversion. The
FeOH moiety is nearly coplanar with the benzene ring. TS2 is
a transition state in which Fe-C bond breaking and C-O bond
formation occur in a concerted manner to connect the hydroxy
intermediate and the product complex that involves phenol as
a ligand. This three-centered transition state is responsible for
Methane-Methanol and Benzene-Phenol Conversions
Figure 4. Potential energy diagram for the direct benzene hydroxy-
lation on a model of “R-oxygen” of Fe-ZSM-5 zeolite in the quartet
state. Relative energies are in kcal/mol.
the process for a phenyl migration from the iron active center
to the oxygen atom. The breaking Fe-C bond and the forming
C-O bond were computed reasonably well to be 1.999 and
1.730 Å, respectively. The three-centered (Fe,O,C) structure
responsible for the phenyl migration is again nearly orthogonal
with the benzene ring. Let us finally look at the product
complex. Note that the basic structure of the phenol moiety in
the product complex is not significantly changed from that of
free phenol.
We thus conclude that the direct conversion of benzene to
phenol should proceed in a concerted manner, via neither radical
species nor ionic intermediates. Our computational results are,
generally, in good agreement with the proposals of Panov et
al.1 Burch and Howitt29 proposed that the mechanism for the
selective oxidation of benzene involves a radical cation as an
intermediate, but our proposal is different from theirs.
Energetics for the Hydroxylation of Benzene. We show in
Figure 4 a computed energy diagram for the benzene hydroxy-
lation on the model of “R-oxygen”. Because the overall reaction
is 8.6 kcal/mol endothermic on the quartet surface, we predict
that the benzene-phenol conversion should be energetically
more favorable than the methane-methanol conversion (23.9
kcal/mol endothermic). This is likely in good agreement with
the experimental results of Panov et al.1,4 In the initial stages
of the reaction, benzene comes into contact with the iron active
site of the “R-oxygen” model to form the reactant complex.
The binding energy for the reactant complex was predicted to
be 10.2 kcal/mol, which is clearly larger than the value in the
methane case (1.6 kcal/mol), due to the higher reactivity of the
frontier π orbitals of benzene. After the reactant complex is
formed, one of the H atoms of the benzene molecule is
abstracted in a concerted manner via TS1. The barrier height
for this electronic process was computed to be 15.4 kcal/mol
from the reactant complex and 5.2 kcal/mol from the dissociation
limit on the quartet surface. We think that this transition state
should be thermally accessible.
The hydroxy intermediate thus formed is also stable in energy.
Therefore, the barrier height for TS2 was predicted to be very
large (31.1 kcal/mol) if measured from the hydroxy intermediate.
However, from a close inspection of the energy diagram, the
height of TS2 is found to be comparable to the dissociation
limit. If this reaction is kinetically controlled, the energy
difference between the transition state and the dissociation limit
is a good measure in considering whether the reaction takes
place or not. We therefore think that this transition state is also
thermally accessible to lead to the product complex. The energy
required for the desorption of phenol from the complex was
J. Phys. Chem. B, Vol. 104, No. 4, 2000 739
computed to be 20.2 kcal/mol, which is smaller than 26.6 kcal/
mol in the methanol desorption; see Figure 2. Thus, the product
methanol is more strongly bound to the active iron site of Fe-
ZSM-5 zeolite than the product phenol. This computational
result is in good agreement with the statement of Panov et al.4
that the product methanol is strongly bound to the surface of
zeolite and can be extracted by using a mixture of water and
acetonitrile.
Conclusions
The reaction pathways and the energetics for the direct
hydroxylation of methane and of benzene that occur on the
surface of Fe-ZSM-5 zeolite have been computed and analyzed
using the B3LYP DFT method. We proposed a reasonable
model for “R-oxygen”, a surface oxygen species that is
responsible for the catalytic reactivities of Fe-ZSM-5 zeolite;
our model involves an iron-oxo species on the AlO4 surface
site as an active center. The salient features of the two reaction
pathways proposed are identical in essential bonding characters.
In the initial stages of each reaction, methane or benzene comes
into contact with the active iron site of the “R-oxygen” model
leading to the reactant complex. H atom abstraction from
methane or benzene occurs via a four-centered transition state
(TS1), resulting in the formation of the hydroxy intermediate.
The hydroxy intermediate is next transformed into the product
complex via a three-centered transition state (TS2). These
electronic processes take place in a two-step concerted manner
with a stable reaction intermediate. Our proposals for the zeolite-
catalyzed reactions are essentially identical to those for the gas-
phase methane-methanol and benzene-phenol conversions by
the bare iron-oxo complex.9,10 The overall reaction for the
methane hydroxylation is 23.9 kcal/mol endothermic on the
quartet surface and 26.0 kcal/mol endothermic on the sextet
surface, and that for the benzene hydroxylation is 8.6 kcal/mol
endothermic on the quartet surface. Thus, we predict that the
benzene-phenol conversion should be energetically more
favorable than the methane-methanol conversion.
We think that the “two-step concerted mechanism” should
be widely applicable in interpreting how hydrocarbon hydroxy-
lations are catalyzed by transition-metal oxides. The reaction
pathways proposed in this article may have relevance to certain
enzymatic processes concerning hydrocarbon hydroxylations,
in which various iron-oxo complexes play a central role.30,31
Our mechanistic proposals are completely consistent in the gas-
phase,9,10 enzymatic,28 and zeolite-catalyzed reactions.
Acknowledgment. We are grateful to the “Research for the
Future” Program of the Japan Society for the Promotion of
Science (JSPS-RFTF96P00206) and to a Grant-in-Aid for
Scientific Research on the Priority Area “Molecular Biometal-
lics” from the Ministry of Education, Science, Sports, and
Culture of Japan for their support of this work. Y.S. is grateful
to the JSPS for a graduate fellowship. Computations were partly
carried out at the Supercomputer Laboratory of Kyoto University
and at the Computer Center of the Institute for Molecular
Science.
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