Syntheses and Applications of Symmetrical Dinuclear Half-Sandwich Ruthenium(II)–Dipicolinamide Complexes as Catalysts in the Transfer Hydrogenation of Ketones
Abstract
:1. Introduction
2. Results and Discussion
2.1. Synthesis and Characterisation of Ligands and Complexes
2.2. Molecular Structures of Ruthenium(II) Complexes Ru1 and Ru3
2.3. Transfer Hydrogenation of Ketones
2.3.1. Influence of Catalyst Structure on the TH of Acetophenone
2.3.2. Investigation of the Ketone Substrate Scope
3. Conclusions
4. Experimental Section
4.1. Materials and Instrumentations
4.2. X-ray Data Collection, Structure, and Refinement
4.3. Synthesis of Dinuclear Ruthenium(II) Carboxamide Complexes
4.3.1. [{Ru(η6-p-cymene)2-μ-Cl}2L1][Ru(η6-p-cymene)Cl3] (Ru1)
4.3.2. [{Ru(η6-p-cymene)2-μ-Cl}2L1][PF6] (Ru2)
4.3.3. [{Ru(η6-p-cymene)2-μ-Cl}2L2][PF6] (Ru3)
4.3.4. [{Ru(η6-p-cymene)2-μ-Cl}2L3][PF6] (Ru4)
4.3.5. Transfer Hydrogenation of Experiments
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Parameters | Ru1 | Ru4 |
---|---|---|
Empirical formula | C48H54Cl4N4O2Ru3+[CH2Cl2] | C39H42ClF6N4O3PRu2 |
Formula weight | 1418.74 | 997.32 |
Temperature/K | 100 (2) | 100 (2) |
Wavelength(Å) | 1.54178 | 1.54170 |
Crystal system | Triclinic | Monoclinic |
Space group | P-1 | P21/c |
Unit cell dimensions; | ||
a | 13.121 (2)Å | 15.3868 (4) |
b | 15.820 (3)Å | 19.3230 (5) |
c | 16.506 (4)Å | 13.7638 (4) |
α | 61.430 (6)◦ | 90 |
β | 71.530 (11)◦ | 101.771 (1) |
ɣ | 72.142 (7)◦ | 90 |
Volume | 2803.9 (10)Å3 | 4006.18 (19) |
Z | 2 | 4 |
Density (calculated) / Mg/m3 | 1.680 | 1.654 |
Absorption coefficient/ mm−1 | 11.186 | 7.713 |
F(000) | 1424.0 | 200080 |
Crystal Size (mm3) | 0.14 × 0.095 × 0.07 | 0.15 × 0.15 × 0.15 |
Theta range for data collection | 71.961 | 68.225 |
Reflections collected | 11036 | 7297 |
Completeness | 97.6% | 99.4% |
Refinement method | Full-matrix least-square on F2 | Full-matrix least-square on F2 |
Goodness-of-fit on F2 | 1.076 | 1.057 |
Final R indices [I>2sigma(I)] | R1 = 0.0511, wR2 = 0.1447 | R1 = 0.0278, wR2 = 0.0782 |
R indices (all data) | R1 = 0.0567, wR2 = 0.1509 | R1 = 0.0282, wR2 = 0.0785 |
Largest diff. peak and hole/eA−3 | 1.55/−2.57 | 1.42/−0.50 |
Entry | Catalyst Loading/× 10−3 mol% (ppm) | Base | b Conversion[%] | Yield% | TON × 104 | TOF × 103/h−1 |
---|---|---|---|---|---|---|
1 | - | KtBuO | 2 | 1 | - | - |
2 | 5.00 (50) | - | 32 | 30 | 0.64 | 1.07 |
3 | 2.50 (25) | KtBuO | 41 | 39 | 1.56 | 2.60 |
4 | 5.00 (50) | KtBuO | 86 | 85 | 1.72 | 2.87 |
5 | 15.00 (150) | KtBuO | 95 | 94 | 0.63 | 1.05 |
6 | 25.00 (250) | KtBuO | 96 | 95 | 0.26 | 0.43 |
7 | 55.00 (550) | KtBuO | 99 | 98 | 0.13 | 0.22 |
8 | 5.00 (50) | KOH | 76 | 76 | 1.71 | 2.85 |
9 | 5.00 (50) | K2CO3 | 29 | 28 | 0.58 | 0.97 |
Entry | Catalyst | b Conv. [%] | b Yield [%] | TON × 104 | TOF/h−1 x 103 | kobs × 10−1/h−1 |
---|---|---|---|---|---|---|
1 | [RuCl2(p-cymene)2] | 12 | 11 | 0.02 | 0.03 | -- |
2 | Ru1 | 99 | 98 | 1.96 | 3.27 | 1.97 |
3 | Ru2 | 86 | 85 | 1.72 | 2.87 | 1.69 |
4 | Ru3 | 96 | 94 | 1.88 | 3.13 | 1.76 |
5 | Ru4 | 92 | 92 | 1.84 | 3.07 | 1.73 |
Entry | Ketone | b Yield (%) | Entry | Ketone | b Yield% |
---|---|---|---|---|---|
1 | 86 | 8 | 75 | ||
2 * | 99 | 9 | 78 | ||
3 * | 99 | 10 | 88 | ||
4 | 70 | 11 | 84 | ||
5 | 81 | 12 | 76 | ||
6 | 79 | 13 | 73 | ||
7 | 78 | 14 | 88 |
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Kumah, R.T.; Mvelase, S.T.; Ojwach, S.O. Syntheses and Applications of Symmetrical Dinuclear Half-Sandwich Ruthenium(II)–Dipicolinamide Complexes as Catalysts in the Transfer Hydrogenation of Ketones. Inorganics 2022, 10, 190. https://doi.org/10.3390/inorganics10110190
Kumah RT, Mvelase ST, Ojwach SO. Syntheses and Applications of Symmetrical Dinuclear Half-Sandwich Ruthenium(II)–Dipicolinamide Complexes as Catalysts in the Transfer Hydrogenation of Ketones. Inorganics. 2022; 10(11):190. https://doi.org/10.3390/inorganics10110190
Chicago/Turabian StyleKumah, Robert Tettey, Sabathile Thandeka Mvelase, and Stephen Otieno Ojwach. 2022. "Syntheses and Applications of Symmetrical Dinuclear Half-Sandwich Ruthenium(II)–Dipicolinamide Complexes as Catalysts in the Transfer Hydrogenation of Ketones" Inorganics 10, no. 11: 190. https://doi.org/10.3390/inorganics10110190