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1 Oidation reactions catalyzed by osmium compounds. Part 4. Highly efficient oidation of hydrocarbons and alcohols including glycerol by the H 2 O 2 /Os 3 (CO) 12 /pyridine reagent Georgiy B. Shul pin, a, * Yuriy N. Kozlov, a Lidia S. Shul pina, b Wagner A. Carvalho c and Dalmo Mandelli c a Semenov Institute of Chemical Physics, Russian Academy of Sciences, ulitsa Kosygina, dom 4, Moscow , Russia b Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ulitsa Vavilova, dom 28, Moscow , Russia c Center of Natural and Human Sciences, Federal University of ABC (UFABC), Santa Adélia Street, 166, Bangu, Santo André, SP, , Brazil * Corresponding author. Tel.: ; fa: ; ; addresses: Shulpin@chph.ras.ru and gbsh@mail.ru (G.B. Shul pin) Supplementary information S1

2 Concentration of oygenates (M).12 OOH.8.4 O OH Time (h) Fig. S1. Oidation of cyclooctane with H 2 O 2 catalyzed by 1 in the absence of pyridine. Accumulation of cyclooctyl hydroperoide, cyclooctanone, and cyclooctanol with time is shown. Conditions: [cyclooctane] =.5 M, [1] = M, [H 2 O 2 ] = 1.5 M (7% aqueous). Solvent MeCN, 6 C. Concentrations of the three products (cyclooctyl hydroperoide, cyclooctanol and cyclooctanone) were calculated by the comparison of the concentrations of cyclooctanol and cyclooctanone measured before and after reduction with PPh 3 (for this method, see Refs. 7b,8f,9). A dotted line corresponds to the maimum initial rate. Table S1. Oidation of cyclooctane with H 2 O 2 catalyzed by 1 in the presence of different amines a Entry Amine Yield (% based on cyclooctane) after 2 h 8 h 24 h 1 Pyridine Picoline Pyrazine.2 4 2,2 -Bipyridine Imidazole a Conditions: [cyclooctane] =.5 M, [1] = M, [H 2 O 2 ] =.25 M (7% aqueous), [amine] =.2 M. Solvent MeCN, 6 C. S2

3 Initial reaction rate, 1 6 W (M s 1 ) Total concentration of oygenates, c (M) h h [H 2 O 2 ] (M) Fig. S2. Dependence of yield of oygenates after 4 and 8 h on initial concentration of hydrogen peroide in the cyclooctane oidation. Conditions: [cyclooctane] =.5 M, [py] =.1 M, [1] = M, H 2 O 2, 7% aqueous, solvent MeCN, 6 C. Concentration of water in the reaction was maintained constant [H 2 O] = const by adding necessary amounts of H 2 O [H 2 O] total (M) Fig. S3. Dependence of initial reaction rate W on totall concentration of water in the cyclooctane oidation. Conditions were the same as in the eperiment shown in Fig. S2. S3

4 Total concentration of oygenates, c (M) h h [pyridine] (M) Fig. S4. Dependence of yield of oygenates after 4 and 8 h on initial concentration of pyridine in the cyclooctane oidation. Conditions were the same as in the eperiment shown in Fig. 3. Table S2 Cycloheane oidation with H 2 O 2 in acetonitrile catalyzed by various metal complees a Entry Catalyst Concentration Cocatalyst Time TON TON Initial TOF Initial TOF Yield (%) b Ref. (M) (h) (per one ion) (h 1 ) (per one ion)(h 1 ) 1 1 b pyridine This work 2 Cp* 2Os c pyridine c 3 (n-bu 4N)[VO 3] d PCA a, (n-bu 4N)[VO 3] d PCA a, Cu 4 e HCl a 6 Cu-1 f None b 7 [Mn 2L 2O 3][PF 6] g MeCOOH c 8 [Co 4Fe 2OSae 8] b,h HNO d 9 [Co 4Fe 2OSae 8] h HNO d 1 [Co 4Fe 2OSae 8] h HNO d 11 Cp 2Fe i PCA e a Yield was based on cycloheane in cases when its amount was lower than the oidant amount. b Cyclooctane was used instead of cycloheane. с Decamethylosmocene, Cp* is pentamethylcyclopentadienyl. d The efficient oidizing reagent (n-bu 4 N)[VO 3 ]/PCA/H 2 O 2 (PCA is pyrazine-2-carboylic acid) was initially described by one of us in Refs. 9a,13b d. Mechanistic studies demonstrated 14,15 that this system operates with the participation of hydroyl radicals. e Cu 4 is tetracopper(ii) triethanolaminate comple [O<Cu 4 {N(CH 2 CH 2 O) 3 } 4 (BOH) 4 ][BF 4 ] 2. f Cu-1 is comple Cu(MeCN) 4 BF 4 ; t-buooh was used instead of H 2 O 2. g L = 1,4,7-trimethyl-1,4,7-triazacyclononane. h [Co 4 Fe 2 OSae 8 ] is comple [Co 4 Fe 2 OSae 8 ] 4DMF H 2 O, where H 2 Sae = salicylidene-2-ethanolamine. i Ferrocene, Cp is cyclopentadienyl ligand. S4

5 Fig. S5. An eample of the 1 H NMR spectrum of the reaction miture obtained in the glycerol oidation with H 2 O 2 catalyzed by Os 3 (CO) 12 and pyridine. S5

6 A cm 1 cm 1 B Fig. S6. The IR spectra of Os 3 (CO) 12 (precatalyst 1) (graph A) and evaporated stock solution of 1 in MeCN. Both spectra were recorded for the KBr tablet. S6

7 Total yield of oygenates (%) Total yield of oygenates (%) 7 6 A 8 h 7 6 B 8 h h h h 1 1 h Age of the stock solution (days) Age of the stock solution (days) Fig. S7. Oidation of cyclooctane with the H 2 O 2 /Os 3 (CO) 12 (compound 1)/pyridine system using the stock solutions stored previously at room temperature (Graph A) and in the refrigerator (Graph B). Yields of sum of products after 1, 4, and 8 h are shown. Other conditions: [Os 3 (CO) 12 ] = M; [H 2 O 2 ] =.25 M; [pyridine] =.1 M; [cyclooctane] =.5 M; 6 o C. Estimation of alkyl hydroperoide concentration by comparison of chromatograms obtained before and after reduction of the reaction solution with PPh 3 The quantification of alkyl hydroperoides and ketones (aldehydes) and alcohols present in the reaction solution was performed using developed previously by Shul pin 7b,8f,9 simple GC method with reduction of the reaction samples with tryphenylphosphine. Alkyl hydroperoides formed in the oidation of alkanes decompose 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" +... The alcohol/ketone (aldehyde) ratio is usually around 1:1. It should be noted that under mild conditions the alkyl hydroperoide, ROOH, can be easily transformed into the corresponding ketone (or aldehyde), R COR, via dehydratation without formation of the alcohol, ROH. However, at elevated temperature ROOH decomposes via a multistep radical-chain mechanism. Some stages of this process S7

8 afford both products, the ketone and alcohol in the 1:1 ratio (ROOH = RO + HO ; 2ROOH = RO + ROO + H 2 O; ROO + ROO = ROH + R COR + O 2 ; see Ref. 1e, pp. 41, 47). If an ecess of solid PPh 3 is added to a sample of the reaction solution ca. 1 min before GC analysis the alkyl hydroperoide, ROOH, present in the reaction miture is completely reduced to the corresponding alcohol: R'CH(OOH)R" + PPh 3 R'CH(OH)R" + O=PPh 3 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). Measuring a sum of concentrations alcohols+ketone (aldehyde) after reduction with PPh 3 gives us precise value of total concentration of all primary products (that is of alkyl hydroperoide, alcohol and ketone). The comparison of this value with concentrations of the alcohol and ketone (aldehyde) before reduction with PPh 3 allows us to estimate the real concentrations of the alkyl hydroperoide, alcohol, and ketone (aldehyde) in the reaction solution. The oidation of alkane occurs in accord with the following equation RH ROOH + ROH + R'C(=O)R" real y real z real where [ROOH] = real, [ROH] = y real, and [R'C(=O)R"] = z real are real concentrations of the three products in the reaction sample. Injecting the sample directly into chromatograph leads to decomposition of really present in the solution alkyl hydroperoide to give detectable by GC additional concentrations y add and z add of ROH and R'C(=O)R": ROOH ROH + R'C(=O)R" real y add z add Assuming that alkyl hydroperoide decomposes in the GC to produce the corresponding alcohol and ketone in the 1:1 ratio we can calculate the real concnetrations of the three products of alkane oidation using the following equations: [ROOH] = real (z before z after ) + (y after y before ) [ROH] = y real y before (z before z after ) [R'C(=O)R"] = z real = z after S8

9 where y before and z before are the amounts of alcohol and ketone (aldehyde) measured by GC before reduction with PPh 3 ; y after and z after the amounts of alcohol and ketone (aldehyde) measured by GC after reduction with PPh 3, respectively. A more detailed description has been published. 7b S9