Alcohol Oxidation Assisted by Molybdenum Hydrazonato Catalysts Employing Hydroperoxide Oxidants
Abstract
:1. Introduction
2. Results and Discussion
2.1. Catalysts Preparation and Characterization
2.2. Catalytic Results
2.2.1. Carveol Oxidation
2.2.2. Cyclohexanol Oxidation
2.2.3. Butan-2-ol Oxidation
3. Materials and Methods
3.1. Preparative Part
3.1.1. Synthesis of the Polynuclear Molybdenum Complexes
3.1.2. Synthesis of the Mononuclear Molybdenum Complexes
3.2. General Procedure for the Oxidation of Secondary Alcohols
3.2.1. Carveol Oxidation
3.2.2. Cyclohexanol Oxidation
Protocol A
Protocol B
3.2.3. Butan-2-ol Oxidation
Without MeCN (Protocol A)
With MeCN (Protocol B)
3.3. Physical Methods
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Complex | 1 | 2 | 3 | 4 |
---|---|---|---|---|
Atom | Δδ/ppm | |||
C-1 | 8.01 | 7.56 | 7.26 | 6.9 |
C-4 | 5.66 | 5.65 | 4.47 | 4.44 |
C-2′ | 2.04 | 1.96 | 2.02 | 1.88 |
Catalyst | Conversion a/% | Selectivity b/% | TOF20 min c/h−1 | TON d |
---|---|---|---|---|
H2O2 | ||||
1 | 88 | 41 | 113 | 308 |
2 | 87 | 42 | 294 | 339 |
3 | 77 | 40 | 4 | 30 |
4 | 85 | 44 | 34 | 329 |
1a | 87 | 41 | 23 | 36 |
2a | 84 | 41 | 286 | 344 |
3a | 89 | 37 | 27 | 367 |
4a | 91 | 42 | 20 | 394 |
THBP (in water) | ||||
1 | 64 | 10 | 237 | 235 |
2 | 66 | 10 | 29 | 27 |
1a | 62 | 11 | 29 | 27 |
2a | 56 | 19 | 185 | 271 |
THBP (in decane) | ||||
2a | 99 | 4 | 1001 | 289 |
Catalyst | Oxidant | Conversion a/% | Selectivity b/% |
---|---|---|---|
2 | H2O2 | 11 | 64 |
2a | H2O2 | 13 | 59 |
THBP (in water) | 17 | 31 | |
THBP (in decane) | 28 | 59 |
Catalyst | Conversion a/% | Selectivity b/% | TOF20min c/h−1 | TON d |
---|---|---|---|---|
1 | 19 | 59 | 3 | 19 |
2 | 16 | 66 | 2 | 16 |
3 | 20 | 57 | 3 | 31 |
4 | 19 | 61 | 4 | 20 |
1a | 21 | 66 | 4 | 21 |
2a | 15 | 71 | 3 | 15 |
3a | 14 | 68 | 76 | 14 |
4a | 19 | 61 | 4 | 20 |
Catalyst | Oxidant | Conversion a/% | Selectivity b/% | TOF20 min c/h−1 | TON d |
---|---|---|---|---|---|
1a | H2O2 | 11 | 54 | 27 | 43 |
H2O2 + MeCN | 12 | 57 | 31 | 49 | |
TBHP | 17 | 45 | 99 | 52 | |
TBHP + MeCN | 13 | 59 | 170 | 52 | |
2a | H2O2 | 23 | 40 | 44 | 90 |
H2O2 + MeCN | 16 | 61 | 17 | 66 | |
TBHP | 17 | 60 | 104 | 69 | |
TBHP + MeCN | 37 | 57 | 117 | 151 | |
3a | H2O2 | 13 | 64 | 38 | 52 |
H2O2 + MeCN | 13 | 69 | 30 | 52 | |
TBHP | 19 | 51 | 83 | 73 | |
TBHP + MeCN | 15 | 52 | 153 | 54 | |
4a | H2O2 | 14 | 49 | 71 | 55 |
H2O2 + MeCN | 15 | 59 | 91 | 59 | |
TBHP | 16 | 56 | 108 | 64 | |
TBHP + MeCN | 14 | 47 | 26 | 56 |
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Mihalinec, J.; Pajski, M.; Guillo, P.; Mandarić, M.; Bebić, N.; Pisk, J.; Vrdoljak, V. Alcohol Oxidation Assisted by Molybdenum Hydrazonato Catalysts Employing Hydroperoxide Oxidants. Catalysts 2021, 11, 881. https://doi.org/10.3390/catal11080881
Mihalinec J, Pajski M, Guillo P, Mandarić M, Bebić N, Pisk J, Vrdoljak V. Alcohol Oxidation Assisted by Molybdenum Hydrazonato Catalysts Employing Hydroperoxide Oxidants. Catalysts. 2021; 11(8):881. https://doi.org/10.3390/catal11080881
Chicago/Turabian StyleMihalinec, Josipa, Matea Pajski, Pascal Guillo, Mirna Mandarić, Nikol Bebić, Jana Pisk, and Višnja Vrdoljak. 2021. "Alcohol Oxidation Assisted by Molybdenum Hydrazonato Catalysts Employing Hydroperoxide Oxidants" Catalysts 11, no. 8: 881. https://doi.org/10.3390/catal11080881