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Received: 16 December 2009 Revised: 5 February 2010 Accepted: 7 February 2010 Published online in Wiley Interscience:

(www.interscience.com) DOI 10.1002/aoc.1641

Oxidation of alkanes and alcohols with hydrogen peroxide catalyzed by complex Os3(CO)10(-H)2
Georgiy B. Shulpina , Yuriy N. Kozlova , Lidia S. Shulpinab and Pavel V. Petrovskiyb
Trinuclear carbonyl hydride cluster, Os3 (CO)10 (-H)2 , catalyzes oxidation of cyclooctane to cyclooctyl hydroperoxide by hydrogen peroxide in acetonitrile solution. The hydroperoxide partly decomposes in the course of the reaction to afford cyclooctanone and cyclooctanol. Selectivity parameters obtained in oxidations of various linear and branched alkanes as well as kinetic features of the reaction indicated that the alkane oxidation occurs with the participation of hydroxyl radicals. A similar mechanism operates in transformation of benzene into phenol and styrene into benzaldehyde. The system also oxidizes 1-phenylethanol to acetophenone. The kinetic study led to a conclusion that oxidation of alcohols does not involve hydroxyl radicals as main oxidizing species and apparently proceeds with the participation of osmyl species, Os O. Copyright c 2010 John Wiley & Sons, Ltd. Supporting information may be found in the online version of this article. Keywords: alkanes; alcohols; alkyl hydroperoxides; homogeneous catalysis; hydrogen peroxide; hydroperoxidation; ketones; osmium complexes

Introduction
Complexes of various transition metals and particularly organometallic derivatives are well-known catalysts for oxidations of hydrocarbons[1,2] and alcohols[3] with peroxides, predominantly hydrogen peroxide. Osmium derivatives have been reported to efciently catalyze oxidation of olens with peroxides.[4] In contrast, relatively few publications have been devoted to osmiumcatalyzed oxidations of saturated and aromatic hydrocarbons and alcohols.[5,6] Here, we have explored the possibility of complex Os3 (CO)10 (-H)2 to catalyze oxidation of alkanes and alcohols with hydrogen peroxide.

Results and Discussion

We have found that trinuclear carbonyl hydride cluster, Os3 (CO)10 (-H)2 (compound 1, Scheme 1), catalyzes oxidation of cyclooctane (2, Scheme 2) to cyclooctyl hydroperoxide (3), which partly decomposes in the course of the reaction to afford cyclooctanone (4) and cyclooctanol (5) by hydrogen peroxide in acetonitrile solution. The same system oxidizes 1-phenylethanol (6) to acetophenone ( 7). Accumulation of the oxygenates in the oxidation of cyclooctane at two different initial concentrations of catalyst 1 and H2 O2 is shown in Fig. 1. It can bee seen that cyclooctyl hydroperoxide is the main product which decomposes to produce cyclooctanone and cyclooctanol. Concentrations of the three products were measured by GC comparing concentrations of cyclooctanone and cyclooctanol before and after reduction of the reaction mixture with an excess of PPh3 . For this method developed previously;[1a,f,g] see the Experimental. The formation of oxygenates occurs with

pronounced auto-acceleration, which indicates that compound 1 is a precatalyst of this reaction. Catalytically active species are formed during rst hour of the process and after that the reaction proceeds with maximum rate. Maximum yield of products (34%) based on cyclooctane was attained after 6.5 h (Fig. 1, graph A). Maximum turnover number, that is number of moles of products per 1 mol of the catalyst was attained (TON = 1400) after 5 h and maximum turnover frequency (TOF = TON per 1 h) was reached (480 h1 ) between 1 and 2 h (see Fig. 1B). It can be seen that kinetic curves for conditions of experiments shown in Fig. 1(A and B) are quite similar. However, at higher concentrations of 1 (5 104 M; Fig. 1A) the nal yields of all products are higher and the amounts of cyclooctanone and cyclooctanol are also higher. The nature of the alkane oxidizing species can be evaluated if we measure the selectivity parameters in oxidations of certain alkanes (Table 1, entry 1). It can be seen that these parameters are close to the selectivities determined previously for the systems generating hydroxyl radicals (entries 28) and noticeably lower

Correspondence to: Georgiy B. Shulpin, Semenov Institute of Chemical Physics, Kinetics and Catalysis, ul. Kosygina, dom 4, Moscow 119991, Russian Federation. E-mail: gbsh@mail.ru

Part 2 of the series Oxidations catalyzed by osmium compounds. For part 1, see Shulpin et al.[5g] . a Semenov Institute of Chemical Physics, Russian Academy of Sciences, ulitsa Kosygina, dom 4, Moscow 119991, Russia b Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ulitsa Vavilova, dom 28, Moscow 119991, Russia

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G. B. Shulpin et al.
A 0.16 Concentration / M 0.12 0.08 0.04 0 0 B 0.16 Concentration / M 0.12 0.08 0.04 4 0 0 2 4 Time / h 6 5 8 3 2 4 6 4 5 8 3

Figure 1. Accumulation (concentration, M) of cyclooctyl hydroperoxide (3), cyclooctanone (4) and cyclooctanol (5) in the oxidation of cyclooctane (2) with time. Concentrations of these products in the reaction solution were measured by comparison of chromatograms prepared before and after reduction of the samples with an excess of PPh3 (for this method, see Shulpin[1a,f,g] and Experimental). Conditions: [cyclooctane]0 = 0.5 M; 60 C; solvent, acetonitrile; total volume of the reaction solution, 5 ml. (A) [1]0 = 5104 M, [H2 O2 ]0 = 1.0 M. (B) [1]0 = 1104 M, [H2 O2 ]0 = 1.5 M.

OC OC Os OC OC OC

CO H Os CO 1 H

CO CO Os CO

Scheme 1. Formula of catalyst Os3 (CO)10 (H)2 (1).

H H2O2 precatalyst 1 2 CH3 OH H2O2 3

OOH + 4

O + 5 CH3 O

OH

precatalyst 1 6 7

Oxidation of benzene (0.5 M) with H2 O2 (2 M) in the presence of 1 (5 104 M) during 1 h at 60 C gave phenol (0.05 M, yield 10%) and oxidation of styrene under the same conditions afforded benzaldehyde (0.06 M, yield 13%). These results testify that the oxidation occurs with the participation of hydroxyl radicals. Consumption of 1-phenylethanol in its oxidation and accumulation of acetophenone are shown in Fig. 2. No auto-acceleration can be noticed in this case unlike in the oxidation of cyclooctane. When the hydrogen peroxidealcohol ratio is 2.5, maximum yield (60%) of acetophenone is attained after 10 h (Fig. 2B). If hydrogen peroxide is used in a larger excess (5 : 1) over-oxidation of acetophenone takes place after 6 h (Fig. 2C). We studied the dependences of the initial rate of the transformation of 1-phenylethanol to acetophenone W0 on initial concentrations of the reactants. Rate W0 linearly depends on concentration of pre-catalyst 1 (Fig. 3). The dependence of W0 on initial concentration of 1-phenylethanol is shown in Fig. 4(B). It is noteworthy that initial rate increases if some amount of water is added to the reaction solution (Fig. 5). Finally, W0 practically does not depend on initial concentration of hydrogen peroxide at [H2 O2 ]0 > 1 M if total concentration of water is maintained constant (9 M) (Fig. 6). Let us discuss a possible mechanism of oxidation of alkanes and alcohols. The catalytic system under consideration demonstrates at the rst glance contradictory properties. On the one hand, low selectivity parameters of the alkane oxygenation (see Table 1) allow us to assume that a species oxidizing alkanes is hydroxyl radicals. On the other hand, it is doubtful that a high degree of phenylethanol conversion to acetophenone (see Fig. 2B) can be attained in the case of attack of hydroxyl radicals at 1-phenylethanol containing reactive phenyl substituent. Indeed, the analysis of data given in Farhataziz[8] shows that the probability of the interaction between radical HO and the benzene ring is higher than that between HO and the alcohol group. Because of this, one could expect the formation in this case of large amounts of oxidative transformation of the benzene ring. In contrast, the real yield of such products is not high. Thirdly, the mode of the dependence of W0 for 1-phenylethanol oxidation on its initial concentration (see Fig. 4A) is not in accordance with the assumption that the alcohol oxidation occurs with the participation of hydroxyl radicals. It is known that in the case of oxidations with the participation of hydroxyl radicals (for example, for the systems H2 O2 h, H2 O2 vanadatePCA in acetonitrile, see Shulpin et al.[2t,7a,d,e] ), even when substrates react with HO with the rate constant lower that that for 1-phenylethanol, value W0 practically does not depend on substrate concentration if this concentration is higher than ca 0.5 M. It follows from the data demonstrated in Fig. 4(A) that the rate of 1-phenylethanol oxidation on catalyst 1 continues to grow even at [6]0 > 0.5 M, despite the rate constant of the interaction between 6 and HO being approximately one order of magnitude higher than the corresponding constant for cyclohexane. Let us assume that the dependence shown in Fig. 4(A) corresponds to the competition for the oxidizing species X between 1-phenylethanol (6) and a component P of the reaction mixture: reagents X Wi k1 k2 (i) (1) (2)

Scheme 2. Oxidation of cyclooctane (2) and 1-phenylethanol (6).

than parameters determined for the systems oxidizing without the participation of reactive radicals (entries 912).

X+6 7 X + P products

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Oxidation of alkanes and alcohols with hydrogen peroxide

Table 1. Selectivity parameters in H2 O2 oxidations of alkanes by certain catalytic systemsa C(1) : C(2) : C(3) : C(4) Entry 1 2 3 4 5 6 7 8 9 10 11 12 13
a

1 : 2 : 3 MCH 1 : 6.5 : 18 1:2:6 1 : 9 : 37 1 : 7 : 15 1 : 6 : 23 1 : 9 : 18 1 : 6 : 113 1 : 116 : 255 1 : 26 : 200 1 : 0.3 : 06 no products Isooctane 1 : 5 : 12 1:3:6 1:4:9 1:2:4 1:4:7 1:4:7 1 : 4 : 30 1 : 10 : 240 1 : 5 : 50 1 : 0.4 : 32 1 : 0 : 41 no products cis-1,2-DMCH 0.9 0.9 1.3 0.75 0.8 0.9 0.9 0.34 0.2 no products

trans/cis trans-1,2-DMCH 0.9 1.0 1.2 0.8 0.8 0.9 0.9 4.1 7.3 no products

Catalytic system 1 h b Fe(SO4 )2 b VO3 /PCAc Ni(ClO4 )2 /Ld,e Al(NO3 )3 f Al2 O3 g Ti-MMM-2h NaAuCl4 i [Mn2 L2 (O)3 ]2+ /MeCO2 Hd,j [Mn2 L2 (O)3 ]2+ /(COOH)2 k,l Cu(NCCH3 )4 BF4 k,m TS-1n

n-Heptane 1 : 6.5 : 7 : 6 1 : 10 : 7 : 6 1 : 5 : 5 : 4.5 1:6:7:5 1:6:7:6 1:5:5:5 1 : 4.5 : 4 : 3.5 1 : 9 : 7 : 6.5 1 : 35 : 25 : 23 1 : 46 : 35 : 34 1 : 14 : 13 : 12 1 : 14 : 9 : 13 1 : 80 : 193 : 100

Parameter C(1) : C(2) : C(3) : C(4) is relative normalized (calculated taking into account the number of hydrogen atoms at each carbon) reactivities of hydrogen atoms at carbons 1, 2, 3 and 4 of the chain of n-octane or n-heptane. Parameter 1 : 2 : 3 is relative normalized reactivities of hydrogen atoms at primary, secondary and tertiary carbons of methylcyclohexane and isooctane. Parameter trans/cis is the ratio of isomers of tert-alcohols with mutual trans- and cis-orientation of the methyl groups formed in the oxidation of cis- and trans-1,2-dimethylcyclohexane. All parameters were measured after reduction of the reaction mixtures with triphenylphosphine before GC analysis and calculated based on the ratios of isomeric alcohols. b See Shulpin et al.[7a] c For this system, see Kozlov et al.[2t] and Shulpin et al.[7b e] d L is 1,4,7-trimethyl-1,4,7-triazacyclononane. e For this system, see Shulpin et al.[7f] f For this system, see Mandelli et al.[7g] g For this system, see Mandelli et al.[7h] h For this system, see Bonon et al.[2g] i For this system, see Shulpin et al.[7i] j For this system, see Shulpin et al.[2d,p 7j,k] k tert-Butylhydroperoxide is used instead of H2 O2 . l For this system, see Shulpin et al.[7l,m] m For this system, see Shulpin et al.[7n] n For this system, see Shulpin et al.[7o,p]

R'=O ROH 1 H2O2 W1 "Os=O" H2O2 RH "OsOOH" H2O2 "Os=O" + O2 + H2O + H+

. "Os=O" + HO RH W2 . R ROOH

Scheme 3. Proposed reaction pathways in the oxidation of alkane RH and alcohol ROH with hydrogen peroxide catalyzed by complex 1.

where Wi is the rate of generation of species X by the catalytic system. The analysis of this kinetic scheme leads to equation (3): d[6] d[7] = = dt dt Wi k2 [P] 1+ k1 [6] (3)

Equation (3) satisfactorily describes the experimantally obtained data (see Fig. 4B). From the dependence shown in Fig. 4(B)

and equation (3), it follows that k2 [P]/k1 = 0.6. Assuming that P is acetonitrile (for its oxidation[9] ), we calculate k2 /k1 = 0.035. If we assume that P is hydrogen peroxide this ratio is k2 /k1 = 0.3. The k2 /k1 ratios are 7 104 and 2.5 103 for the interactions of acetonitrile and hydrogen peroxide, respectively, with hydroxyl radicals. It can be seen that in our case both values are substantially higher (50 and >120 times, respectively) than the corresponding k2 /k1 ratios for the reactions with the participation of hydroxyl

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G. B. Shulpin et al.
A 100 80 Amount / % 60 40 20 0 0 B 100 80 Amount / % 5 10 15
Figure 3. Dependence of the initial rate of acetophenone accumulation in the oxidation of 1-phenylethanol on the initial concentration of catalyst 1. Conditions: [1-phenylethanol]0 = 1.6 M, [H2 O2 ]0 = 2.0 M, [H2 O]total = 7.2 M, 60 C.

105W0 / M s1

60 40 20 0 0 0.5 1.0 1.5 2.0 2.5 3.0 103 [1]0 / M

2
60
104 / M 1 s W0

40

1
20 0 0 5 10 15 105 W0 / M s1 8

6 4 2

1 [6]0

5 / M 1

10

100 80

1
0 0 1.2 0.4 0.8 [1-phenylethanol]0 / M 1.6

Amount / %

60 40 20 0 0 5 Time / h 10 15

Figure 4. Dependence of the initial rate of acetophenone accumulation in the oxidation of 1-phenylethanol on the initial concentration of 1-phenylethanol. Conditions: [H2 O2 ]0 = 2.0 M, [H2 O]total = 7.2 M, [1]0 = 5 104 M, 60 C.

105 W0 / M s1

Figure 2. Consumption of 1-phenylethanol (curve 1) and accumulation of acetophenone (curve 2) in the oxidation of 1-phenylethanol with H2 O2 catalyzed by complex 1 under different conditions. (A) [1-phenylethanol]0 = 1.6 M, [H2 O2 ]0 = 2.0 M, [H2 O]total = 7.2 M, [1]0 = 5 104 M. (B) [1-phenylethanol]0 = 0.4 M, [H2 O2 ]0 = 1.0 M, [H2 O]total = 3.6 M, [1]0 = 5 104 M. (C) [1-phenylethanol]0 = 0.4 M, [H2 O2 ]0 = 2.0 M, [H2 O]total = 7.2 M, [1]0 = 5 104 M. The solvent was acetonitrile (total volume of the reaction solution was 5 ml), 60 C.

[H2O]added / M 0 15 10 5 0 0 5 10 [H2O]total / M 15 5 10

radicals. These calculations support again that the main species inducing the 1-phenylethanol oxidation is not the hydroxyl radical. Some decrease of W0 at [H2 O2 ]0 > 1.5 M is apparently due to the concurrent interaction of species X with 1-phenylethanol and hydrogen peroxide. In accordance with proposed kinetic scheme which is reected by equation (3) and the data shown in Fig. 4, the 1-phenylethanol oxidation rate W0 should decrease by 1.2 times when [H2 O2 ]0 increases from 1.5 to 3.0 M. As Fig. 6 shows that this decrease of W0 is approximately equal to 1.25, we can conclude

Figure 5. Dependence of the initial rate of acetophenone accumulation in the oxidation of 1-phenylethanol on the concentration of water. Conditions: [1-phenylethanol]0 = 1.6 M, [H2 O2 ]0 = 1.0 M, [1]0 = 5 104 M, 60 C.

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Oxidation of alkanes and alcohols with hydrogen peroxide

Experimental
105 W0 / M s1 15 10 5 0 0 1 2 [H2O2]0 / M 3

Figure 6. Dependence of the initial rate of acetophenone accumulation in the oxidation of 1-phenylethanol on the initial concentration of hydrogen peroxide at constant concentration of water. Conditions: [1-phenylethanol]0 = 1.6 M, [1]0 = 5 104 M, [H2 O]total = const = 10.8 M, 60 C.

that our assumption about the concurrent interaction of X with 1-phenylethanol and H2 O2 is supported by the experimental data. Fourthly, the oxidation rate of 1-phenylethanol is 510 times higher than the rate of cyclooctane oxidation catalyzed by 1. Taking into account all features discussed above, we can assume that during hydrogen peroxide decomposition catalyzed by complex 1 oxidizing species of two different types are generated with different rates. One of these species is hydroxyl radical, which oxidizes alkanes. Another species is apparently an osmyl species containing Os O bonds. This species is much less reactive in comparison with hydroxyl radical and it is unable to efciently attack alkanes, RH, but it can react with an alcohol, ROH. The generation rate of the osmyl species is 510 times higher than the generation rate of hydroxyl radical. Based on this model of our oxidizing system (Scheme 3), we can say that the selectivity parameters of alkane oxidation are governed by the reaction with hydroxyl radicals whereas the rate of 1-phenylethanol oxidation as well as the yield of the products are limited mainly by the process of the osmyl species generation (W1 / W2 > 5). There is also some interaction between 1-phenylethanol and hydroxyl radicals. However the increment of this pathway into the total oxidation process is not substantial; the dominating route is with the participation of the Os O species. Scheme 3 reects the competition between 1-phenylethanol and hydrogen peroxide for the primary oxidizing species Os O, which is generated by the catalytic system. Species Os O is a derivative of low-valence (II, III or IV) osmium formed from 1 under the action of H2 O2 , and it is possibly stabilized by acetonitrile ligands. Similar species have been recently synthesized and characterized.[10] This scheme takes into account also the formation of hydroxyl radicals in the course of further transformations of the Os O. These further steps of the reaction induce the oxidation of alkanes but they do not play a crucial role in the alcohol oxidation due to low rate of hydroxyl radical generation. The scheme also considers the catalase decomposition of hydrogen peroxide which is substantial at low concentration of 1-phenylethanol.

Triosmium carbonylhydride, H2 Os3 (CO)10 (precatalyst 1; for synthesis and properties of this compound, see ref.[11] ) was used in the form of a stock solution in acetonitrile (typically, concentration [1]0 in the stock solution was 103 M). The reactions of alkanes or 1-phenylethanol were typically carried out in air in thermostated Pyrex cylindrical vessels with vigorous stirring and using MeCN as solvent. Precatalyst 1 was introduced into the reaction mixture in the form of a stock solution in acetonitrile. The substrate (alkane or 1-phenylethanol) was then added and the reaction started when hydrogen peroxide (50% in H2 O) was introduced in one portion. (CAUTION: compound 1 is toxic and should therefore be handled with care. All reactions should be carried out in a fume hood. The combination of air or molecular oxygen and H2 O2 with organic compounds at elevated temperatures may be explosive!) After certain time intervals samples (about 0.2 ml) were taken. The reactions with alkanes were stopped by cooling and after addition of nitromethane as a standard compound analyzed by GC. In order to determine concentrations of all alkane (cyclooctane) oxidation products the samples of reaction solutions were analyzed twice (before and after their treatment with PPh3 ) by GC (Chromatograph-3700, fused silica capillary column FFAP/OV101 20/80 w/w, 30 m 0.2 mm 0.3 m; helium as a carrier gas) measuring concentrations of alkanol and alkanone. For details of this method developed previously, [1a,f,g] see the Appendix. Authentic samples of all oxygenated products were used to attribute the peaks in chromatograms (comparison of retention times was carried out for different regimes of GC-analysis). Blank experiments showed that, in the absence of precatalyst 1, only very low amounts of products were formed. Concentrations of products obtained in the oxidation of 1-phynylethanol, benzene and styrene after certain time intervals were measured using 1 H NMR method (acetone-d6 was added to the samples; Bruker AMX- 400 instrument, 400 MHz). For the determination of concentrations of substrates and products, corresponding signals were integrated using added 1,4-dinitrobenzene as a standard. Acknowledgment This work was supported by the Russian Foundation for Basic Research (grant no. 06-03-32344-a). Supporting information Supporting information may be found in the online version of this article.

References
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Conclusions
This study demonstrates that oxidations of alkanes and alcohols by the 1H2 O2 system proceed via different mechanisms with participation of either hydroxyl radicals or osmyl species Os O.

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G. B. Shulpin et al.
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Phys. Lipids 2010, 163, 165; b) G. B. Shulpin, Y. N. Kozlov, L. S. Shulpina, A. R. Kudinov, D. Mandelli, Inorg. Chem. 2009, 48, 10480; c) S.-M. Yiu, W.-L. Man, T.C. Lau, J. Am. Chem. Soc. 2008, 130, 10821; d) T. Iida, S. Ogawa, K. Hosoi, M. Makino, Y. Fujimoto, T. Goto, N. Mano, J. Goto, A. F. Hofmann, J. Org. Chem. 2007, 72, 823; e) S. Ogawa, K. Hosoi, T. Iida, Y. Wakatsuki, M. Makino, Y. Fujimoto, A. F. Hofmann, Eur. J. Org. Chem. 2007, 3555; f) Q. Yuan, W. Deng, Q. Zhang, Y. Wang, Adv. Synth. Catal. 2007, 349, 1199; g) G. B. Shulpin, A. R. Kudinov, L. S. Shulpina, E. A. Petrovskaya, J. Organometal. Chem. 2006, 691, 837; h) L. S. Shulpina, A. R. Kudinov, E. A. Petrovskaya, T. V. Strelkova, G. B. Shulpin, Petrol. Chem. 2006, 46, 164; i) T. Osako, E. J. Watson, A. Dehestani, B. C. Bales, J. M. Mayer, Angew. Chem. Int. Ed. 2006, 45, 7433; j) B. C. Bales, P. Brown, A. Dehestani, J. M. Mayer, J. Am. Chem. Soc. 2005, 127, 2832; k) S.-M. Yiu, Z.-B. Wu, C.-K. Mak, T.-C. Lau, J. Am. Chem. 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41, 405; m) Y. N. Kozlov, G. V. Nizova, G. B. Shulpin, J. Phys. Org. Chem. 2008, 21, 119; n) G. B. Shulpin, J. Gradinaru, Y. N. Kozlov, Org. Biomol. Chem. 2003, 1, 3611; o) G. B. Shulpin, T. Sooknoi, V. B. Romakh, G. Suss-Fink, L. S. Shulpina, Tetrahedron Lett. 2006, 47, 3071; p) G. B. Shulpin, T. Sooknoi, L. S. Shulpina, Petrol. Chem. 2008, 48, 36. [8] Farhataziz, A. B. Ross Selected Specic Rates of Reactions of Transients from Water in Aqueous Solution. III. Hydroxyl Radical and Perhydroxyl Radical and their Radical Ions, NSRDS-NBS 59, Washington, DC, 1977. [9] a) Y. N. Kozlov, G. V. Nizova, G. B. Shulpin, J. Mol. Catal. A: Chem. 2005, 227, 247; b) G. Suss-Fink, G. V. Nizova, S. Stanislas, G. B. Shulpin, J. Mol. Catal. A: Chem. 1998, 130, 163. [10] a) K. C. Fortner, D. S. Laitar, J. Muldoon, L. Pu, S. B. Braun-Sand, O. Wiest, S. N. Brown, J.Am.Chem.Soc. 2007, 129, 588; b) A. Ishikawa, Y. Nakao, H. Sato, S. Sakaki, Inorg. Chem. 2009, 48, 8154. [11] a) C. Li, W. K. Leong, J. Coll. Interface Sci. 2008, 328, 29; b) J. L. G ratea Morales, J. M. Fern ndez-G., Organometallics 2004, 23, 3840; c) S.a G. Ang, X. Zhong, H.-G. Ang, J. Organometal. Chem. 2003, 665, 218; d) S.-G. Ang, X. Zhong, H.-G. Ang, Inorg. Chem. 2002, 41, 3791; e) L. P. Clarke, J. E. Davies, P. R. Raithby, M.-A. Rennie, G. P. Shields, E. Sparr, J. Organometal. Chem. 2000, 609, 169; f) H. D. Kaesz, Inorg. Synth. 1990, 28, 238.

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G. B. Shulpin et al.

Appendix: Estimation of Amounts of Alkyl Hydroperoxide, Alcohol, and Ketone or Aldehyde by a Gc Method Using Triphenylphosphine and Pyridine
Oxygenation of alkanes by molecular oxygen or peroxides in air usually gives rise to the formation of the corresponding alkyl hydroperoxides as the main primary products. The quantication of alkyl hydroperoxides and ketones (aldehydes) and alcohols present in the reaction solution can be performed by a simple GC method which uses tryphenylphosphine. This method has been developed earlier.[1a,f,g] Alkyl hydroperoxides formed in various oxidations of alkanes by O2 or H2 O2 are decomposed in the chromatograph to afford corresponding alcohols and ketones (aldehydes) as main products: R CH(OOH)R R CH(OH)R + R C( O)R + . . . (A1)

The alcohol/ketone (aldehyde) ratio is usually around 1 : 1. The exact value of this ratio depends on the construction of the injector, its material, temperature of the injector, etc. It depends also on the nature and amount of the catalyst used in the oxidation reaction as this catalyst is injected in a very small amount into the instrument. Many reactions between the components can occur in the injector. Decomposition of ROOH produces not only the alcohol and ketone but also affords various derivatives obtained in the CC bond rapture processes. The reaction of the products with non-consumed in the reaction H2 O2 is also possible in the injector. As a consequence, the chromatogram shows many small peaks in addition to the main peaks of the alcohol and ketone. As mentioned above, typically alkyl hydroperoxide decomposes in the gas chromatograph to afford the corresponding alcohol and ketone (aldehyde) in the ca 1 : 1 ratio. However, under specic conditions, this ratio can be substantially different. For example, if pyridine is present in the reaction mixture this base induces the transformation of the hydroperoxide into ketone:
N-base R'C( O)R + H2O

sum obtained after the reduction. However, in some cases (when the extensive decomposition of various peroxides occurs in the injector before the reduction) the sum of concentrations alcohol + ketone before the reduction is lower than that obtained after the reduction. It is evidently, that the analysis after the reduction gives more precise quantication of products because PPh3 reduces ROOH to ROH quantitatively. Also in some cases (quartz-lined injector and silica capillary columns of GC instrument) peaks of the alkyl hydroperoxide can be detected in addition to the peaks of the alcohol and ketone. However, the peaks of ROOH can be observed only very seldom when the hydroperoxide decomposes only partly (this is possible if the injector is free from the traces of the catalyst used in the oxidation; after two or three injections the accumulated in the injector catalyst begins to decompose ROOH completely). Thus, determination of a sum of concentrations alcohols + ketone (aldehyde) after reduction with PPh3 gives us precise value of total concentration of all primary products (that is of alkyl hydroperoxide, alcohol and ketone). The comparison of this value with concentrations of the alcohol and ketone (aldehyde) before reduction with PPh3 allows us to estimate the real concentrations of the alkyl hydroperoxide, alcohol and ketone (aldehyde) in the reaction solution. It should be noted that it is incorrect to make any conclusions on the existence or non-existence of the alkyl hydroperoxide on the basis of the chromatogram obtained only after the reduction with PPh3 . Indeed, in the absence of ROOH in the reaction mixture all amount of the alcohol determined by GC could be equal to the real amount of the alcohol present in the reaction solution. If the amounts of the alcohol and ketone determined before PPh3 reduction are exactly equal to the amounts measured after reduction this fact testies that no alkyl hydroperoxide is present in the reaction solution. How can we estimate quantitatively concentrations of alkyl hydroperoxide, ROOH, alcohol, ROH, and ketone or aldehyde, R C( O)R formed in the oxidation of alkane, RH? Let us suppose that real concentrations of the three products in the reaction sample are the following: [ROOH] = xreal ,

R'CH(OOH)R

(A2)

[ROH] = yreal , [R C( O)R ] = zreal , that is, the oxidation of RH gives the followong real concentrations of the products: RH ROOH ROH R C( O)R + + yreal zreal xreal (A4)

As a result the ketone : alcohol ratio can be raised to 8 : 1 (see Fig. S1a in ref.[5b] ). If an excess of solid PPh3 is added to a sample of the reaction solution ca 10 min before GC analysis the alkyl hydroperoxide, ROOH, present in the reaction mixture is completely reduced to the corresponding alcohol: R CH(OOH)R + PPh3 R CH(OH)R + O PPh3 (A3)

In this case, the chromatogram differs from that of a sample not subjected to the reduction (the alcohol peak rises, while the intensity of the ketone peak decreases). The phosphine reduces not only ROOH but also oxidizing reagent (H2 O2 ) and thus no parasite oxidation reactions become possible in the injector. In addition, the phosphine reduces all primary product|s of the peroxidic nature, and due to this reduction no products obtained in the injector via decomposition of peroxidic compounds are seen. In many cases (if in the injection before the reduction only small amounts of peroxides give products of various rearrangements) the sum of concentrations alcohol + ketone before the reduction is equal to the same

Now we should introduce some restrictions: (i) no reaction occurs between H2 O2 and RH in the injector of chromatograph; (ii) the alkyl hydroperoxide is completely decomposed in chromatograph giving only additional portions of the alcohol and ketone (aldehyde). If we inject the sample directly into chromatograph all really present in the solution alkyl hydroperoxide is decomposed to give detectable by GC additional concentrations yadd and zadd of ROH and R C( O)R : ROH R C( O)R ROOH + yadd zadd xreal (A5)

As we discussed above, the yadd /zadd ratio depends on the material of the chromatograph and conditions of the GC analysis,

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Oxidation of alkanes and alcohols with hydrogen peroxide inlcuding the inuence of some components of the reaction solution, especially of a catalyst. Let us suppose that yadd =m zadd (A6) Using the last equations we can easily deduce formulae for the real concentrations of the three products expressed via concentrations of the alcohol and ketone measured before and after reduction with PPh3 : [ROOH] = xreal = m(zbefore zafter ) + (yafter ybefore ) (A23) [ROH] = yreal = ybefore m(zbefore zafter ) [R C( O)R ] = zreal = zafter (A24) (A25)

Parameter m can be measured experimentally via injection of a solution of pure specially synthesized ROOH under identical conditions. Concentrations of the alcohol and ketone (aldehyde) measured by GC before reduction with PPh3 will be the following: ybefore = yreal + yadd zbefore = zreal + zadd (A7) (A8)

If we assume (or determine experimentally) that m 1 we will obtain a simple formulae: [ROOH] = xreal (zbefore zafter ) + (yafter ybefore ) (A26) [ROH] = yreal ybefore (zbefore zafter ) [R C( O)R ] = zreal = zafter (A27) (A28)

In the case when we reduce the sample with PPh3 after this procedure taking into account reaction (A9) ROH ROOH + PPh3 yadd xreal and expression (A10) yadd = xreal (A9)

(A10)

the GC analysis will give the following measured concentrations: yafter = yreal + yadd = yreal + xreal , zafter = zreal In summary, we have the following system of equations: ybefore = yreal + yadd zbefore = zreal + zadd yafter = yreal + xreal zafter = zreal yadd =m zadd (A13) (A14) (A15) (A16) (A17) (A11) (A12)

Taking into account the ability of alkyl hydroperoxides to decompose in the chromatograph in the presence of pyridine (see Fig. S1a in Shulpin et al.[5b] ) to produce mainly or exclusively the corresponding ketone or aldehyde we can propose an alternative method for estimation of real concentrations of the three products, ROOH, ROH and R C( O)R . This method allows us to avoid the determination of parameter m in equation (A6). Let us consider again reactions (A29 A2) and (A30 A9):
pyridine R'CH(OOH)R xreal R'C( O)R + H2O zadd*

(A29)

ROOH ROH + PPh3 + OPPh3 xreal yadd

(A30)

Subtracting equation (A16) from equation (A14) we obtain the expression (A18) zbefore zafter = zadd Taking into account that yadd = mzadd we come to equations (A20) and (A21A15). ybefore = yreal + mzadd = yreal + m(zbefore zafter ) yafter = yreal + xreal (A20) (A21) (A19)

The GC analysis of the reaction mixture which contains pyridine gives us measured concentrations of the alcohol and ketone ywithpy and zwithpy . Assuming that reaction (A29) is the quantitative transformation of the alkyl hydroperoxide to the ketone in chromatograph in the presence of pyridine and reaction (A30) is the quantitative reduction of ROOH by PPh3 we will come to the following equations: ywithpy = yreal zwithpy = zreal + zadd = zreal + xreal yafter = yreal + yadd = yreal + xreal zafter = zreal

(A31) (A32) (A33) (A34)

Now we can easily obtain the equations which allow us to calculate real concentrations of the three products: [ROOH] = xreal = zwithpy zafter = yafter ywithpy (A35) [ROH] = yreal = ywithpy [R C( O)R ] = zreal = zafter (A36) (A37)

Subtracting equation (A21) from equation (A20) we obtain ybefore yafter = m(zbefore zafter ) xreal (A22)

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