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84858466175
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1H NMR in two different coordinating solvents, acetonitrile and DMSO. For a 9.2 mM solution of 1, the monomer to dimer ratios were determined to be 1.0:1.5 and 1.0:3.3 in acetonitrile and DMSO, respectively. This solvent-dependent equilibrium implies that the monomer exists as a solvate.
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1H NMR in two different coordinating solvents, acetonitrile and DMSO. For a 9.2 mM solution of 1, the monomer to dimer ratios were determined to be 1.0:1.5 and 1.0:3.3 in acetonitrile and DMSO, respectively. This solvent-dependent equilibrium implies that the monomer exists as a solvate.
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-1.
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-1.
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48
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84858476436
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After 24 h, the rate of aerobic oxidation of 2-heptanol catalyzed by either 1 or 4 was negligible due to complete decomposition of the catalyst. The TON for 1 (∼12) was higher than the TON for 4 (∼9) because, in addition to decomposing to 5, complex 4 has a second decomposition pathway; 4 is unstable in solution and decomposes to an unidentified species on the same time scale as the reaction.
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After 24 h, the rate of aerobic oxidation of 2-heptanol catalyzed by either 1 or 4 was negligible due to complete decomposition of the catalyst. The TON for 1 (∼12) was higher than the TON for 4 (∼9) because, in addition to decomposing to 5, complex 4 has a second decomposition pathway; 4 is unstable in solution and decomposes to an unidentified species on the same time scale as the reaction.
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0037010004
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Mori, K.; Yamaguchi, K.; Hara, T.; Mizugaki, T.; Ebitani. K.; Kaneda, K. J. Am. Chem. Soc. 2002, 124, 11572.
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-1.
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-1.
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51
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84858477672
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Other phenanthroline catalysts11 are believed to exhibit rate-limiting β-hydride elimination
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11 are believed to exhibit rate-limiting β-hydride elimination.
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52
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84858477667
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30,31
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30,31
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36249003574
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At room temperature, the 1H NMR spectrum of 4 (7.4 mM in 1:1 acetonitrile-d3/dimethyl sulfoxide-d6) indicates that only a single species is present. While we suspect that this species is the dimer 4, we have not yet ruled out its assignment as monomeric 4
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6) indicates that only a single species is present. While we suspect that this species is the dimer 4, we have not yet ruled out its assignment as monomeric 4.
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36248975549
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Although water does create an equilibrium between 1, 4, and acetic acid, a very large excess of water is required to produce appreciable amounts of 4. Therefore, the formation of 4 (due to the water produced in the reaction) cannot account for the entirety of the rate decrease with time observed for catalysis with 1
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Although water does create an equilibrium between 1, 4, and acetic acid, a very large excess of water is required to produce appreciable amounts of 4. Therefore, the formation of 4 (due to the water produced in the reaction) cannot account for the entirety of the rate decrease with time observed for catalysis with 1.
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36248929120
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The limit of detection for hydrogen peroxide by this method was estimated to be 0.5 mM (see the Supporting Information).
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The limit of detection for hydrogen peroxide by this method was estimated to be 0.5 mM (see the Supporting Information).
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These disproportionation catalysts include catalase enzyme (1:1 water/acetonitrile), silver(I) oxide, manganese(II) oxide, and palladium/ calcium carbonate. The use of either potassium iodide or sodium thiosulfate resulted in precipitation of a palladium complex.
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These disproportionation catalysts include catalase enzyme (1:1 water/acetonitrile), silver(I) oxide, manganese(II) oxide, and palladium/ calcium carbonate. The use of either potassium iodide or sodium thiosulfate resulted in precipitation of a palladium complex.
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During the course of the aerobic 2-heptanol oxidation, dimer 4 appears as a precipitate in the reaction mixture. Dimer 4 eventually redissolves, presumably by reaction with alcohol or acetic acid, to regenerate 1.
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During the course of the aerobic 2-heptanol oxidation, dimer 4 appears as a precipitate in the reaction mixture. Dimer 4 eventually redissolves, presumably by reaction with alcohol or acetic acid, to regenerate 1.
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2 (2) at higher temperatures (80 °C, 30 bar of air), did not report ligand oxidation. This may be due to the different reaction conditions (presence of sodium acetate) or the faster rate of hydrogen peroxide (or palladium hydroperoxide) disproportionation at these higher temperatures.
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2 (2) at higher temperatures (80 °C, 30 bar of air), did not report ligand oxidation. This may be due to the different reaction conditions (presence of sodium acetate) or the faster rate of hydrogen peroxide (or palladium hydroperoxide) disproportionation at these higher temperatures.
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