Heterometallic CoIIIZnII Schiff Base Catalyst for Mild Hydroxylation of C(sp3)–H Bonds of Unactivated Alkanes: Evidence for Dual Mechanism Controlled by the Promoter
Abstract
:1. Introduction
2. Results and Discussion
2.1. Synthesis and crystal structure
2.2. Spectroscopic characterization
2.3. Catalytic activity
3. Materials and Methods
3.1. Reagents and General Procedures
3.2. Synthesis of [CoZnL3Cl2]·CH3OH (1)
3.3. Single-crystal X-ray diffraction
3.4. Catalytic oxidation of alkanes
3.5. Catalytic Reactions under 18O2 Atmosphere
3.6. Gas Chromatography
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Entry | Promoter | [Cat]0, mol%2 | Yield, %3 | Yield, %4 | cis/trans5 | TON6 | 3° : 2°7 |
---|---|---|---|---|---|---|---|
1 | HNO3 | 0.08 | 17 | 61 | 82 | 198 | 38 : 1 |
2 | HNO3 | 0.8 | 11 | 40 | 82 | 13 | 38 : 1 |
3 | HNO3 | 0.3 | 14 | 50 | 90 | 48 | 38 : 1 |
48 | HNO3 | 0.3 | 37 | 37 | 29 | 56 | 37 : 1 |
5 | HOTf9 | 0.3 | < 1 | < 1 | > 40 | < 1 | ‒ |
6 | TFA10 | 0.3 | 7 | 26 | 16 | 25 | 24 : 1 |
7 | HOAc11 | 0.3 | 6 | 24 | 11 | 25 | 19 : 1 |
8 | PCA12 | 0.3 | < 1 | < 1 | 1 | < 1 | ‒ |
9 | Et3N | 0.3 | 2 | 6 | 1 | 2.2 | ‒ |
10 | Py13 | 0.3 | < 1 | 2 | 2 | 5.4 | ‒ |
1114 | HNO3 | 0.3 | 14 | 51 | 78 | 59 | 40 : 1 |
1215 | HNO3 | 0.3 | 10 | 36 | 59 | 36 | 32 : 1 |
Entry | Substrate | Yield based on m-CPBA, %2 | cis/trans | 3° : 2° |
---|---|---|---|---|
1 | cis-1,2-DMCH | 50 | 90 | 38 : 1 |
2 | cis-1,4-DMCH | 64 | 42 | 22 : 1 |
3 | trans-1,2-DMCH | 46 | 623 | 13 : 1 |
4 | trans-1,4-DMCH | 49 | 373 | 12 : 1 |
5 | Adamantane | 714 | – | 39 : 1 |
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Nesterova, O.V.; Kasyanova, K.V.; Buvaylo, E.A.; Vassilyeva, O.Y.; Skelton, B.W.; Nesterov, D.S.; Pombeiro, A.J.L. Heterometallic CoIIIZnII Schiff Base Catalyst for Mild Hydroxylation of C(sp3)–H Bonds of Unactivated Alkanes: Evidence for Dual Mechanism Controlled by the Promoter. Catalysts 2019, 9, 209. https://doi.org/10.3390/catal9030209
Nesterova OV, Kasyanova KV, Buvaylo EA, Vassilyeva OY, Skelton BW, Nesterov DS, Pombeiro AJL. Heterometallic CoIIIZnII Schiff Base Catalyst for Mild Hydroxylation of C(sp3)–H Bonds of Unactivated Alkanes: Evidence for Dual Mechanism Controlled by the Promoter. Catalysts. 2019; 9(3):209. https://doi.org/10.3390/catal9030209
Chicago/Turabian StyleNesterova, Oksana V., Katerina V. Kasyanova, Elena A. Buvaylo, Olga Yu. Vassilyeva, Brian W. Skelton, Dmytro S. Nesterov, and Armando J.L. Pombeiro. 2019. "Heterometallic CoIIIZnII Schiff Base Catalyst for Mild Hydroxylation of C(sp3)–H Bonds of Unactivated Alkanes: Evidence for Dual Mechanism Controlled by the Promoter" Catalysts 9, no. 3: 209. https://doi.org/10.3390/catal9030209