ISSN 0023-1584, Kinetics and Catalysis, 2008, Vol. 49, No. 3, pp. 371–378. © MAIK “Nauka /Interperiodica” (Russia), 2008. Original Russian Text © T.A. Trubitsyna, O.A. Kholdeeva, 2008, published in Kinetika i Kataliz, 2008, Vol. 49, No. 3, pp. 392–399.
Kinetics and Mechanism of the Oxidation of 2,3,6-Trimethylphenol with Hydrogen Peroxide in the Presence of Ti-Monosubstituted Polyoxometalates T. A. Trubitsyna and O. A. Kholdeeva Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630090 Russia e-mail:
[email protected] Received May 29, 2007
Abstract—The product composition and reaction kinetics are reported for 2,3,6-trimethylphenol (TMP) oxidation with hydrogen peroxide in acetonitrile catalyzed by a Ti-monosubstituted polyoxometalate (Ti-POM) with a Keggin structure ([Bu4N]4[PTi(OMe)W11O39]) and for the stoichiometric reaction between TMP and the peroxo complex [Bu4N]4[HPTi(O)2W11O39] (I). The main products of the stoichiometric reaction are 2,3,5-trimethyl-1,4-benzoquinone (TMBQ) and 2,2',3,3',6,6'-hexamethyl-4,4'-biphenol (BP). The TMBQ yield increases as the TMP/I molar ratio is decreased. The catalytic reaction is first-order with respect to H2O2 and the catalyst and has a variable order (1–0) with respect to TMP. The rate of the reaction increases as the water concentration in the reaction mixture is raised. The stoichiometric reaction is first-order with respect to peroxo complex I and has a variable order (1–0) with respect to TMP. There is no kinetic isotope effect for this reaction (kArOH/kArOD = 1). A TMP oxidation mechanism is suggested, which includes the coordination of a TMP molecule and peroxide on a Ti site of the catalyst with the formation of a reactive intermediate. The one-electron oxidation of TMP in this intermediate yields a phenoxyl radical. The subsequent conversions of these ArO• radicals yield the reaction products. DOI: 10.1134/S0023158408030087
The selective catalytic oxidation of organic substrates with aqueous hydrogen peroxide, an environmentally friendly and rather cheap oxidizer, is a promising way of synthesizing oxygen-containing compounds. Microporous and mesoporous materials containing isolated titanium(IV) ions effectively catalyze selective oxidation reactions involving ç2é2 [1–9]. Three liquidphase oxidation process catalyzed by microporous titanium silicate TS-1 (developed by EniChem S.p.A., Italy) have already been commercialized to date [1–3, 8]. Although considerable progress has been made in elucidating the origin of the activity and selectivity of TS-1 and other titanium-containing catalysts by experimental and theoretical methods [10–27], there are many unclear points in the structure of the active sites and in the chemical interaction on the molecular level. It is often easier to detect active species and to determine their structure in solution than to do the same in the solid phase. For this reason, increasing attention is being focused on the mechanisms of catalysis by homogeneous model systems [28–35]. However, mechanistic studies of oxidation reactions using transition-metal complexes with organic or organoelement ligands as soluble model compounds are complicated by oxidative and hydrolytic destruction processes and by oligomerization or polymerization of these complexes [36, 37]. Polyoxometalates (POMs), which are built of metal oxide clusters, are thermodynamically stable against
oxidation and against hydrolysis in a certain pH range [38]. Some authors note that there is a structural analogy between POMs and the metal oxide surface and view POMs as discrete soluble fragments of a metal oxide lattice [39–49]. We have synthesized a number of titanium-monosubstituted POMs with a Keggin structure [50–55], including the protonated peroxo complex [Bu4N]4[HPTi(O)2W11O39] (I), in which the peroxo group is η2-coordinated. This complex is active in the oxidation of organic substrates (thioethers and alkylphenols) [53, 55]. It was suggested that Ti-POMs be used as molecular models in mechanistic studies of oxidation on Ti sites isolated in an inorganic matrix [51−57]. Here, we report the kinetics and mechanism of the catalytic oxidation of 2,3,6-trimethylphenol (TMP) with aqueous hydrogen peroxide in the presence of [Bu4N]4[PTi(OMe)W11O39], a model Ti-POM, and the stoichiometric reaction between TMP and peroxo complex I. The oxidation of TMP with hydrogen peroxide, which can be carried out efficiently on mesoporous titanium silicate catalysts [9, 58–66], is now viewed as an environmentally friendly alternative to the existing methods of obtaining 2,3,5-trimethyl-1,4-benzoquinone (TMBQ), which is a semiproduct in the synthesis of vitamin E. In order to control the selectivity of this reaction, it is essential to gain a detailed understanding of its mechanism.
371
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EXPERIMENTAL Acetonitrile (Fluka) was dried over the activated molecular sieve 4 Å. TMP (Fluka) was recrystallized from hexane. Deuterated TMP (ArOD) was obtained using D2O with a D content of 99.9 at %. The hydrogen peroxide concentration in its solution (~30%) was determined by iodometric titration immediately before use. The synthesis of the polyoxometalate [Bu4N]4[PTi(OMe)W11O39] is described in [67]; the synthesis of the protonated titanium peroxo complex [Bu4N]4[HPTi(O)2W11O39] (I), in [55]. The other chemicals were reagent- or analytical-grade and were used as received. The oxidation of TMP was carried out in a temperature-controlled (±0.2 K) glass reactor in an acetonitrile medium at 80°ë. The reaction was initiated by adding 0.11–0.35 M ç2é2 to a reaction mixture containing 0.1–0.5 M TMP, 0.005–0.04 M catalyst, an internal standard (biphenyl), and MeCH (the total volume of the reaction mixture was 1 ml). The dependence of the reaction rate on the H2O2 concentration was studied by varying the amount of aqueous H2O2 added at a fixed ç2é concentration (1.0 M) for standardization of the reaction conditions. The TMP concentration in the reaction mixture was monitored by GLC. The stoichiometric oxidation of TMP was carried out at 40°ë and [TMP] = 0.1–1.6 M and [I] = 0.02 M. The reaction was monitored by 31P NMR spectroscopy (applied to I) and GLC (applied to TMP). The partial orders of the reaction were determined by studying the dependence of the initial TMP consumption rate on the concentration of one of the reactants at fixed concentrations of the other reactants. The initial rates were determined with an accuracy of 5–7%. The kinetic isotope effect was studied by adding D2O (2.0 M) instead of ç2é (2.0 M) to the reaction mixture 10 min before the initiation of the reaction. The isotope exchange reaction ArOH + D2O ArOD + HDO proceeds rapidly and can readily be monitored by 1H NMR [60]. TMP oxidation products were identified by 1H NMR and mass spec-
trometry. The TMBQ yield and the TMP conversion were determined by GLC. GLC analyses were carried out on a Tsvet-500 chromatograph equipped with a flame ionization detector and a capillary column (25 m × 0.3 mm) packed with Carbowax 20M (Ar, 110–230°C, 10 K/min). GC/MS analyses were performed on a Saturn 2000 gas chromatograph equipped with a CP-3800 mass spectrometer. 1H and 31P NMR spectra were recorded on a DPX250 Bruker spectrometer operating at 250.13 and 161.98 MHz, respectively. Chemical shifts (δ) were measured relative to 85% H3PO4 and tetramethylsilane. The error in δ was ±0.04 ppm for 31P and ±0.01 ppm for 1H. RESULTS AND DISCUSSION Catalytic Oxidation of TMP Earlier, we established that the activity of T-POMs in TMP oxidation with hydrogen peroxide in MeCN decreases in the order [Bu4N]4[PTi(OH)W11O39] > [Bu4N]7[{PTiW11O39}2OH] ~ [Bu4N]8[{PTiW11é39}2O] > [Bu4N]4[PTi(OMe)W11O39] [Bu4N]5PTi(é)W11O39 [50]. The TMP oxidation rate correlates with the formation rate of protonated peroxo complex I in the reaction between the corresponding Ti-POM and ç2é2. In turn, the formation rate of the peroxo complex correlates with the rate of Ti-POM hydrolysis yielding [Bu4N]4[PTi(OH)W11O39], which contains a highly reactive terminal Ti–OH bond [50]. The existence of these correlations suggests that the Ti-POMs react with hydrogen peroxide via a two-step mechanism consisting of a hydrolysis step and a subsequent reaction between Ti–OH and ç2é2 yielding peroxo complex I. The main products of TMP oxidation in the presence of a Ti-POM, as in the presence of titanium silicate catalysts [9, 60], are TMBQ, a C–C coupling product (2,2',3,3',6,6'-hexamethyl-4,4'-biphenol (BP)), and a C–O coupling product (4-phenoxyphenol (PP)). The formation of some amounts of resins also takes place.
OH
O H2O2/Cat MeCN, 80°C
O TMBQ
TMP
+ HO
OH + HO
BP
O
PP KINETICS AND CATALYSIS
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KINETICS AND MECHANISM OF THE OXIDATION OF 2,3,6-TRIMETHYLPHENOL
Identical product distributions are observed for different Ti-POM forms under given conditions. At 80°C, [TMP] = 0.1 M, [ç2é2] = 0.35 M, and [[Bu4N]4[PTi(OMe)W11O39]] = 0.006 M. In 30 min the substrate conversion is complete and the TMBQ yield is about 40%. Note that, for both homogeneous and heterogeneous titanium catalysts, the product distribution depends strongly on the substrate/catalyst ratio: the larger [TMP]/[Ti], the higher the BP yield [55, 59]. The formation of the C–C coupling product indicates that the reaction proceeds via a homolytic mechanism including the intermediate formation of phenoxyl radicals [68].
TMP consumption, %
100 3 80
4
2 1
60 40 20 0 0
The rate of TMP oxidation with hydrogen peroxide in the presence of a Ti-POM is independent of whether the reaction is conducted in the light or in the dark and, also, in an argon atmosphere or in air. Furthermore, it does not change upon the addition of a small amount (0.005 mmol) of a free radical scavenger (2,6-di-tertbutyl-4-methylphenol or hydroquinone) to the reaction mixture. These findings indicate that the reaction takes place via a nonchain or a short-chain mechanism.
10
20
30 40 Time, min
Fig. 1. TMP consumption kinetics in TMP oxidation with hydrogen peroxide in the presence of the Ti-POM and various amounts of water (mol/l): (1) 1.3, (2) 4.0, (3) 6.8, and (4) 12.3; [TMP] = 0.1 mol/l, [[Bu4N]4[PTi(OMe)W11O39]] = 0.01 mol/l, [ç2é2] = 0.35 mol/l, 80°C, MeCN medium.
Note that a similar kinetics was observed for TMP oxidation with hydrogen peroxide catalyzed by mesoporous T–Si catalysts [9, 60]. Since TMP oxidation with hydrogen peroxide in the presence of homogeneous Ti-POMs and the same process in the presence of heterogeneous Ti–Si catalysts yield the same product and obey the same rate laws, it is possible to use TiPOMs as molecular models in detailed studies of the oxidation mechanism.
Typical TMP consumption curves for TMP oxidation with ç2é2 in the presence of the polyoxometalate [Bu4N]4[PTi(OMe)W11O39] are presented in Fig. 1. These kinetic curves show no induction period. The reaction rate increases as the H2O concentration in the reaction mixture is increased (Fig. 1), and the observed order of the reaction with respect to water is ~0.4. At high water concentrations (12.3 M), one cannot rule out the effect of the changed polarity and dielectric constant of the medium on the reaction rate. The dependences of the initial TMP oxidation rate on the catalyst, oxidizer, and substrate concentrations are plotted in Figs. 2–4, respectively. The reaction is first-order with respect to the concentrations of Ti-POM (Fig. 2) and ç2é2 (Fig. 3) and has a variable order (1–0) with respect to the phenolic substrate concentration (Fig. 4).
Interaction between TMP and the Peroxo Complex [Bu4N]4[HPTi(O)2W11O39] (I) Peroxo complex I reacts readily with TMP at 40°C in MeCN to yield TMBQ and/or BP. The product ratio depends on the molar ratio of the reactants. When TMP is in twofold molar excess, the main reaction product is BP (~90%). When I is in twofold excess, the main reaction product is TMBQ (~95%):
[TMP]/[I] = 2
OH
373
+ [Bu4N]4[HPTi(O)2W11O39]
MeCN, 40°C
HO
OH 90%
O
[I]/[TMP] = 2
95% O
These data are consistent with the stoichiometries 1 : 2 and 2 : 1 for TMP oxidation by the peroxo complex to BP and TMBQ, respectively. As was mentioned above, the formation of BP, which is a typical product of one-electron TMP oxidation, suggests that the reacKINETICS AND CATALYSIS
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tion proceeds via a homolytic mechanism involving the formation of phenoxyl radicals (ArO•) [68]. The recombination of these radicals yields BP, and their further oxidation yields TMBQ, which is the product of fourelectron TMP oxidation:
374
TRUBITSYNA, KHOLDEEVA
w0, mol l –1 min –1
w0, mol l –1 min –1 0.008
0.0025 0.0020
0.006
0.0015
0.004
0.0010
0.002
0.0005 0 0
0 0
0.001
0.002
0.003
0.15
0.30
0.004
0.45 0.60 [H2O2], mol/l
[[Bu4N]4[PTi(OMe)W11O39]], mol/l Fig. 2. Initial rate of the catalytic oxidation of TMP with hydrogen peroxide as a function of the Ti-POM concentration ([TMP] = 0.1 mol/l, [H2O2] = 0.35 mol/l, 80°C, MeCN).
•
ArO
ArOH
I
HO
OH O
ArO•
I
O
The oxidation of the phenol is due only to the active oxygen of the peroxo complex, as is indicated by the fact that the reaction rates in an inert atmosphere (Ar) and in air are equal. The complex I consumption kinetic curve and the corresponding logarithmic anamorphosis are presented in Fig. 5. The fact that the anamorphosis is linear, at least until the conversion of I is 60%, is evidence that the reaction is first-order with respect to the peroxo complex. The dependence of the initial TMP oxidation rate on the phenol concentration (Fig. 6) indicates that the order of the reaction with respect to the organic substrate is variable (1–0). The observed rate law of the stoichiometric reaction is consistent with the mechanism involving the formation of reactive intermediate II, which contains both a peroxo group and a TMP molecule: O Ti
+ ArOH OH
k0
K
O OH Ti
Fig. 3. Initial rate of the catalytic oxidation of TMP with hydrogen peroxide as a function of the ç2é2 concentration ([TMP] = 0.1 mol/l, [Bu4N]4[PTi(OMe)W11O39] = 0.01 mol/l, 80°C, MeCN).
Unfortunately, we have not yet detected intermediate II by spectroscopic methods, possibly because the chemical shifts (δ) of the 31P NMR signals from II and the other Ti–POMs are similar. Earlier, we demonstrated that [Bu4N]4[PTi(OH)W11O39], [Bu4N]8[{PTiW11é39}2O], [Bu4N]4[PTi(OMe)W11O39], and [Bu4N]5PTi(é)W11O39 are characterized by nearly identical δ values [50]. The absence of a kinetic isotope effect (kArOD/kArOH = 1) suggests that the most likely ratelimiting step of the oxidation process is not hydrogen atom abstraction from TMP, but the intrasphere transfer of an electron in intermediate II, which yields a phenoxyl radical. w0, mol l –1 min –1 0.0025 0.0020 0.0015 0.0010 0.0005 0 0
OAr H II ArO• + TiO• + H2O.
0.1
0.2
0.3
0.4
0.5 0.6 [íåP], mol/l
Fig. 4. Initial rate of the catalytic oxidation of TMP with hydrogen peroxide as a function of the substrate concentration ([H2O2] = 0.35 mol/l, [Bu4N]4[PTi(OMe)W11O39] = 0.01 mol/l, 80°C, MeCN). KINETICS AND CATALYSIS
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16 14
–5
12
–6
10
–7
8
–8
6
–9
4
0
10
20
30 40 Time, min
50
60
ln([Bu4N]4[HPTi(O)2W11O39])
[(Bu4N)4HPTi(O)2W11O39] × 103, mol/l
KINETICS AND MECHANISM OF THE OXIDATION OF 2,3,6-TRIMETHYLPHENOL
X–TiOH + LOH,
X– Ti
3
0.8
1.2 1.6 [íåP], mol/l
–
H+ + ArOH
X– Ti
(I)
–
H+ + H2O;
0.4
O
where L = Ti, Si, Me, etc., and X = POM or a silicate matrix; η2 hydroperoxo complex formation, X–TiOH + H2O2
6
TMP coordination,
The plot of 1/w0 versus 1/[ArOH] is presented in Fig. 7. Using the straight line equation 1/w0 = 1/k0K[TiOOH][ArOH] + 1/k0[TiOOH], it is possible to estimate the formation constant of the reactive intermediate (K) and the conversion rate constant of this intermediate (k0): K = 4.6 ± 0.1 l/mol and k0 = (9.3 ± 0.3) × 10–4 s–1. Earlier, we demonstrated that the reaction between a Ti-POM and ç2é2 proceeds via a two-step mechanism: the first step is hydrolysis yielding a highly reactive form of TiOH, and the second step is a rapid reaction between this TiOH and H2O2 yielding a titanium peroxo complex [50]. The results of our model kinetic study using the Ti-POM suggest that the mechanism of alkylphenol oxidation with H2O2 on one-site titanium catalysts includes the following basic steps: Hydrolysis,
O
9
Fig. 6. Initial rate of the stoichiometric oxidation of TMP with the peroxo complex as a function of the TMP concentration ([Bu4N]4[HPTi(O)2W11O39] = 0.02 mol/l, 40°ë, MeCN).
k 0 K [ TiOOH ] [ ArOH ] -. w = ---------------------------------------------------1 + K [ ArOH ]
K2
12
0
Thus, the reaction obeys the following rate law:
K1
w0 × 106, mol l –1 s –1
0
70
Fig. 5. Kinetics of the consumption of the peroxo complex [Bu4N]4[HPTi(O)2W11O39] in its stoichiometric reaction with TMP ([TMP] = 0.2 mol/l, 40°C, MeCN); ln([Bu4N]4[HPTi(O)2W11O39]) versus time.
X–Ti–OL + H2O
(II)
O
K3
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OOH
(III)
X– Ti
O
OAr H
Intrasphere electron transfer, OOH X– Ti
k4
OAr• + X–TiO• + H2O;
(IV)
OAr H
ArO• oxidation yielding benzoquinone (BQ), ArO•
····
TiOOH
BQ;
(V)
ArO• recombination yielding BP and PP, 2ArO•
BP and PP;
(VI)
Catalytic cycle closure, ArO•
ArOH or
X–TiO• + H2O
or
X–TiOH + HO•
or
H2O2
(VII)
or
HO2•
Assuming that reactions (I)–(III) rapidly come to equilibrium, we obtain the following equation for the TMP oxidation rate:
k 4 C 0 K 1 K 2 K 3 [ H 2 O 2 ] [ ArOH ] -, w = ---------------------------------------------------------------------------------------------------------------------------------------------------K 1 K 2 K 3 [ H 2 O 2 ] [ ArOH ] + K 1 K 2 [ H 2 O 2 ] + K 1 [ H 2 O ] + [ LOH ] KINETICS AND CATALYSIS
375
(1)
376
TRUBITSYNA, KHOLDEEVA
where C0 is the total concentration of the active sites of the catalyst. Equation (1) predicts that methanol (LOH) admixtures will inhibit TMP oxidation. This effect was actually observed in our earlier work [60] for TMP oxidation with hydrogen peroxide on a titanium silicate catalyst. At the same time, Eq. (1) predicts that the TMP oxidation rate will decrease with an increasing water concentration in the system. In fact, as was mentioned above, the opposite trend is observed experimentally (Fig. 1). Some authors assume the existence of equilibrium between the η1-peroxo and η2-peroxo forms of the titanium hydroperoxo complex [69, 70]: OOH
–
H+
X– Ti
K8
O
–
H+ + H2O.
X– Ti
(VIII)
O η2
OH η1
It is this complex, not its equilibrium counterpart η2, that reacts with a phenol molecule to yield a reactive intermediate: OOH
X–TiOH + H2O2
OOH
–
OH K10
X– Ti
(IX)
OH η1
OOH
–
H3O+.
X– Ti OAr
(X) It is known from the literature that, in the absence of water, the protons are located directly on bridging oxygen atoms of the heteropoly anions, while, in the presence of water, the ç+ ions exist as a constituent of the ion pair [POM]–[ç3é]+ [71]. The conversion of this intermediate yields the reaction products: OOH X– Ti OArOH k11
H+.
H+ + ArOH
X– Ti
It can be assumed that the reaction between the TiOH form and ç2é2 occurs via the formation of the η1-peroxo complex: K9
–
–
H3O+
(XI)
OAr• + X–TiO• + 2H2O.
Assuming that the reaction occurs according to this scheme, we arrive at the following expression for the TMP oxidation rate:
k 11 C 0 K 9 K 10 [ H 2 O ] [ H 2 O 2 ] [ ArOH ] -. w = -----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------K 1 K 9 K 10 [ H 2 O ] [ H 2 O 2 ] [ ArOH ] + K 1 K 9 [ H 2 O ] [ H 2 O 2 ] + K 1 K 9 K 8 [ H 2 O 2 ] + K 1 [ H 2 O ] + LOH Equation (2) provides a plausible explanation for the observed kinetics of TMP oxidation (partial orders of the reaction) and is similar to the rate equation derived
(2)
earlier for TMP oxidation with hydrogen peroxide on a heterogeneous titanium silicate catalyst [60].
0.12
Thus, this model study has revealed a similarity between the oxidation reactions of TMP in the presence of homogenous catalysts (Ti-POMs) and heterogeneous titanium silicate catalysts. It has proved the earlier hypothesis that the oxidation mechanism includes the equilibrium hydrolysis step yielding the Ti–OH form and the equilibrium formation of a reactive intermediate containing a hydroxo group and a TMP molecule. Furthermore, the above kinetic data indicate that titanium η1-peroxo complex is involved in the formation of this reactive intermediate.
0.10
ACKNOWLEDGMENTS
1/w0 × 10–6, s l mol–1 0.16 0.14
0.08 0
1
2
3
4 5 1/[íåP]0, l/mol
Fig. 7. 1/w0 (w0 is the initial rate of stoichiometric TMP oxidation) versus 1/[TMP] ([Bu4N]4[HPTi(O)2W11O39] = 0.02 mol/l, 40°ë, MeCN).
The authors thank Cand. Sci. V.A. Rogov and Cand. Sci. A.V. Golovin for help in GC/MS analyses and 31P and 1H NMR measurements, respectively. This work was supported by the Russian Foundation for Basic Research (grant no. 04-03-32113). T.A. Trubitsyna acknowledges financial support from the K.I. Zamaraev Foundation. KINETICS AND CATALYSIS
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KINETICS AND MECHANISM OF THE OXIDATION OF 2,3,6-TRIMETHYLPHENOL
REFERENCES 1. Centi, G. and Perathoner, S., in Encyclopedia of Catalysis, Horvath, I.T., Ed., New York: Wiley-Interscience, 2003, vol. 6, p. 239. 2. Notari, B., Adv. Catal., 1996, vol. 41, p. 253. 3. Perego, C., Carati, A., Ingallina, P., Mantegazza, M.A., and Bellussi, G., Appl. Catal., A, 2001, vol. 221, p. 63. 4. Tanev, P.T., Chibwe, M., and Pinnavaia, T., Nature, 1994, vol. 368, p. 321. 5. Sayari, A., Chem. Mater., 1996, vol. 8, p. 1840. 6. Corma, A., Chem. Rev., 1997, vol. 97, p. 2373. 7. Trong, OnD., Desplantier-Giscard, D., Danumah, C., and Kaliaguine, S., Appl. Catal., A, 2001, vol. 222, p. 299. 8. Clerici, M.G., “Oxidation and Functionalisation: Classical and Alternative Routes and Sources,” Proc. DGMK/SCI Conf., Milan, 2005, p. 165. 9. Kholdeeva, O.A. and Trukhan, N.N., Usp. Khim., 2006, vol. 75, no. 5, p. 460 [Russ. Chem. Rev. (Engl. Transl.), vol. 75, no. 5, p. 411]. 10. Boccuti, M.R., Rao, K.M., Zecchina, A., and Leofanti, G., Stud. Surf. Sci. Catal., 1989, vol. 48, p. 133. 11. Geobaldo, E., Bordiga, S., Zeccina, A., Giamelo, E., Leofanti, G., and Petrini, G., Catal. Lett., 1992, vol. 16, p. 109. 12. Bordiga, S., Coluccia, S., Lamberti, C., Marchese, L., Zecchina, A., Boscherini, F., Buffa, F., Genoni, F., Leofanti, G., Petrini, G., and Vlaic, G., J. Phys. Chem., 1994, vol. 98, p. 4125. 13. Zecchina, A., Bordiga, S., Lamberti, C., Ricchiardi, G., Scarano, D., Petrini, G., Leofanti, G., and Mantegazza, M.A., Catal. Today, 1996, vol. 32, p. 97. 14. Bolis, V., Bordiga, S., Lamberti, C., Zecchina, A., Carati, A., Rivetti, F., Spano, G., and Petrini, G., Langmuir, 1999, vol. 15, p. 5753. 15. Tozzola, G., Mantegazza, M.A., Ranghino, G., Petrini, G., Bordiga, S., Ricchiardi, G., Lamberti, C., Zulian, R., and Zecchina, A., J. Catal., 1998, vol. 179, p. 64. 16. Thomas, J.M. and Sankar, G., Acc. Chem. Res., 2001, vol. 34, p. 571. 17. Munakata, H., Oumi, Y., and Miyamoto, A., J. Phys. Chem. B, 2001, vol. 105, p. 3493. 18. Zecchina, A., Bordiga, S., Spoto, G., Damin, A., Berlier, G., Bonino, F., Prestipino, C., and Lamberti, C., Top. Catal., 2002, vol. 21, p. 67. 19. Bordiga, S., Damin, A., Bonino, F., Ricchiardi, G., Lamberti, C., and Zecchina, A., Angew. Chem., Int. Ed. Engl., 2002, vol. 41, no. 24, p. 4734. 20. Barker, C.M., Gleeson, D., Kaltsoyannis, N., Catlow, C.R.A., Sankar, G., and Thomas, J.M., Chem. Phys. Phys. Chem, 2002, vol. 4, p. 1228. 21. Prestipino, C., Bonino, F., Usseglio, S., Damin, A., Tasso, A., Clerici, M. G., Bordiga, S., D’Acapito, F., Zecchina, A., and Lamberti, C., Chem. Phys. Phys. Chem, 2004, vol. 5, p. 1799. 22. Bonino, F., Damin, A., Ricchiardi, G., Ricci, M., Spano, G., D’Aloisio, R., Zecchina, A., Lamberti, C., Prestipino, C., and Bordiga, S., J. Phys. Chem. B, 2004, vol. 108, p. 3573. 23. Karlsen, E. and Schoffel, K., Catal. Today, 1996, vol. 32, p. 107. KINETICS AND CATALYSIS
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2008
377
24. Sinclair, P.E. and Catlow, C.R.A., J. Phys. Chem. B, 1999, vol. 103, p. 1084. 25. Yudanov, I.V., Gisdakis, P., Di Valentin, C., and Rosch, N., Eur. J. Inorg. Chem., 1999, vol. 12, p. 2135. 26. Zhidomirov, G.M., Yakovlev, A.L., Milov, M.A., Kachurovskaya, N.A., and Yudanov, I.V., Catal. Today, 1999, vol. 51, p. 397. 27. Sever, R.R. and Root, T.W., J. Phys. Chem., 2003, vol. 107, p. 4090. 28. Feher, F., J. Am. Chem. Soc., 1986, vol. 108, p. 3850. 29. Arzoumanian, H., Baldi, A., Lay, R., Pierrot, M., Petrignani, J.F., Ridouane, F., Sanchez, J., and Krentzien, H., The Role of Oxygen in Chemistry and Biochemistry, Studies in Organic Chemistry, vol. 33, Ando, W. and Moro-oka, Y., Eds., Amsterdam: Elsevier, 1988, p. 227. 30. Basset, J.-M., Candy, J.-P., Choplin, A., Didillon, B., Quignard, F., and Theolier, A., in Perspectives in Catalysis, Thomas, J.M. and Zamaraev, K.I., Eds., Oxford: Blackwell, 1991, p. 125. 31. Edelmann, F.T., Angew. Chem., Int. Ed. Engl., 1992, vol. 31, p. 586. 32. Basset, J.-M., Lefebvre, F., and Cantini, C., Coord. Chem. Rev., 1998, vols. 178–180, p. 1703. 33. Lorenz, V., Fischer, A., Giemann, S., Gilje, J.W., Gun’ko, Y., Jacob, K., and Edelmann, F.T., Coord. Chem. Rev., 2000, vols. 206–207, p. 321. 34. Roesky, H.W., Haiduc, I., and Hosmane, N.S., Chem. Rev., 2003, vol. 103, p. 2579. 35. Fandos, R., Otero, A., Rodriguez, A., Ruiz, M.J., and Trreros, P., Angew. Chem., Int. Ed. Engl., 2001, vol. 40, p. 2884. 36. Bortolini, O., Di Furia, F., and Modena, G., J. Mol. Catal., 1982, vol. 16, p. 61. 37. Talsi, E.P. and Babushkin, D.E., J. Mol. Catal. A: Chem., 1996, vol. 106, p. 179. 38. Pope, M.T., Heteropoly and Isopoly Oxometalates, New York: Springer, 1983. 39. Baiker, L.C.W., in Advances in the Chemistry of the Coordination Compounds, Kirschner, S., Ed., New York: Macmillan, 1961, p. 604. 40. Kazanskii, L.P., Torchenkova, E.A., and Spitsyn, V.I., Usp. Khim., 1974, vol. 43. 41. Day, V.W. and Klemperer, W.G., Science, 1985, vol. 228, p. 533. 42. Finke, R.G. and Droege, M.W., J. Am. Chem. Soc., 1984, vol. 106, p. 7274. 43. Finke, R.G. and Rapko, B., Organometallics, 1986, vol. 5, p. 175. 44. Fournier, M., Louis, C., Che, M., Chaquin, P., and Masure, D., J. Catal., 1989, vol. 119, p. 400. 45. Pope, M.T., Müller A, Angew. Chem., Int. Ed. Engl., 1991, vol. 30, p. 34. 46. Chen, Q. and Zubieta, J., Coord. Chem. Rev., 1992, vol. 114, p. 107. 47. Baker, L.C.W. and Glick, D.C., Chem. Rev., 1998, vol. 98, p. 3. 48. Finke, R.G., Rapko, B., Saxton, R.J., and Domaille, P.J., J. Am. Chem. Soc., 1986, vol. 108, p. 2947. 49. Mohs, T.R., Du, Y., Plashko, B., and Maatta, E.A., Chem. Commun., 1997, p. 1707.
TRUBITSYNA, KHOLDEEVA 62. Kholdeeva, O.A., Trukhan, N.N., Vanina, M.P., Romannikov, V.N., Parmon, V.N., Mrowiec-Bia l on , J., and Jarzebski, A.B., Catal. Today, 2002, vol. 75, p. 203. 63. Trukhan, N.N., Romannikov, V.N., Shmakov, A.N., Vanina, M.P., Paukshtis, E.A., Bukhtiyarov, V.I., Kriventsov, V.V., Danilov, I.Yu., and Kholdeeva, O.A., Microporous Mesoporous Mater., 2003, vol. 59, p. 73. 64. Mrowiec-Bia l on , J., Jarzebski, A.B., Kholdeeva, O.A., Trukhan, N.N., Zaikovskii, V.I., Kriventsov, V.V., and Olejniczak, Z., Appl. Catal., A, 2004, vol. 273, p. 47. 65. Kholdeeva, O.A., Melgunov, M.S., Shmakov, A.N., Trukhan, N.N., Kriventsov, V.V., Zaikovskii, V.I., and Romannikov, V.N., Catal. Today, 2004, vols. 91–92, p. 205. 66. Kholdeeva, O.A., Ivanchikova, I. D., Guidotti, M., and Ravasio, N., Green Chem. (in press). 67. Knoth, W.H., Domaille, P.J., and Roe, D.C., Inorg. Chem., 1983, vol. 22, p. 198. 68. Taylor, W.I., Oxidative Coupling of Phenols, New York: Marcel Dekker, 1967. 69. Prestipino, C., Bonino, F., Usseglio, S., Damin, A., Tasso, A., Clerici, M. G., Bordiga, S., D’Acapito, F., Zecchina, A., and Lamberti, C., Chem. Phys. Chem., 2004, vol. 5, p. 1799. 70. Bonino, F., Damin, A., Ricchiardi, G., Ricci, M., Spano, G., D’Aloisio, R., Zecchina, A., Lamberti, C., Prestipino, C., and Bordiga, S., J. Phys. Chem. B, 2004, vol. 108, p. 3573. 71. Finke, R.G. and Droege, M.W., J. Am. Chem. Soc., 1984, vol. 106, p. 7274. ^
50. Kholdeeva, O.A., Trubitsina, T.A., Maksimov, G.M., Golovin, A.V., and Maksimovskaya, R.I., Inorg. Chem., 2005, vol. 44, p. 1635. 51. Kholdeeva, O.A., Maksimov, G.M., Maksimovskaya, R.I., Kovaleva, L.A., and Fedotov, M.A., React. Kinet. Catal. Lett., 1999, vol. 66, p. 311. 52. Kholdeeva, O.A., Maksimov, G.M., Maksimovskaya, R.I., Kovaleva, L.A., Fedotov, M.A., Grigoriev, V.A., and Hill, C.L., Inorg. Chem., 2000, vol. 39, p. 3828. 53. Kholdeeva, O.A., Kovaleva, L.A., Maksimovskaya, R.I., and Maksimov, G.M., J. Mol. Catal. A: Chem., 2000, vol. 158, p. 223. 54. Kholdeeva, O.A., Maksimovskaya, R.I., Maksimov, G.M., and Kovaleva, L.A., Kinet. Katal., 2001, vol. 42, no. 2, p. 217 [Kinet. Catal. (Engl. Transl.), vol. 42, no. 2, p. 217]. 55. Kholdeeva, O.A., Trubitsina, T.A., Maksimovskaya, R.I., Golovin, A.V., Neiwert, W.A., Kolesov, B.A., López, X., and Poblet, J.-M., Inorg. Chem., 2004, vol. 43, p. 2284. 56. Kholdeeva, O.A., Top. Catal., 2006, vol. 40, p. 229. 57. Kholdeeva, O.A. and Maksimovskaya, R.I., J. Mol. Catal. A: Chem., 2007, vol. 262, p. 7. 58. RF Patent 2164510, 2000. 59. Trukhan, N.N., Romannikov, V.N., Paukshtis, E.A., Shmakov, A.N., and Kholdeeva, O.A., J. Catal., 2001, vol. 202, p. 110. 60. Trukhan, N.N. and Kholdeeva, O.A., Kinet. Katal., 2003, vol. 44, no. 3, p. 378 [Kinet. Catal. (Engl. Transl.), vol. 44, no. 3, p. 347]. 61. RF Patent 2196764, 2001.
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