Synthesis and Catalytic Application of Two Mononuclear Complexes Bearing Diethylenetriamine Derivative Ligand
Abstract
:1. Introduction
2. Results and Discussion
2.1. Synthesis and IR Spectra
2.2. Structure Description of Complex 1
2.3. Structure Description of Complex 2
2.4. PXRD of Complexes 1 and 2
2.5. Catalytic Application on the Henry Reaction
2.5.1. Optimization of Catalytic Reaction Conditions
2.5.2. Expansion of the Substrate Scope on the Henry Reaction
2.5.3. Mechanistic Investigation of the Henry Reaction
3. Materials and Methods
3.1. General
3.2. Synthesis
3.2.1. Synthesis of the Ligand
3.2.2. Synthesis of [NiL(CH3COO)2(H2O)] (1)
3.2.3. Synthesis of [ZnL(CH3COO)2] (2)
3.3. Single-Crystal X-ray Diffraction
3.4. General Procedure for the Henry Reaction
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
References
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Entry | Catalyst Loading b (mol%) | Catalyst | Et3N Loading c (mol%) | Solvent | Yield (%) |
---|---|---|---|---|---|
1 | 6 | 1 + Et3N | 20 | MeOH | 39 |
2 | 8 | 1 + Et3N | 20 | MeOH | 68 |
3 | 10 | 1 + Et3N | 20 | MeOH | 81 |
4 | 12 | 1 + Et3N | 20 | MeOH | 81 |
5 | 14 | 1 + Et3N | 20 | MeOH | 82 |
6 | 10 | 1 + Et3N | 20 | MeOH | 78 |
7 | 10 | 1 | 20 | MeOH | 35 |
8 | 10 | 2 | 20 | MeOH | 33 |
9 | 10 | L | 20 | MeOH | 0 |
10 | 10 | Et3N | 20 | MeOH | 35 |
11 | 10 | Ni(OAc)2 × 4H2O | 0 | MeOH | 19 |
12 | 10 | Zn(OAc)2 × 2H2O | 0 | MeOH | 15 |
13 | 10 | 1 + Et3N | 10 | MeOH | 56 |
14 | 10 | 1 + Et3N | 15 | MeOH | 73 |
15 | 10 | 1 + Et3N | 25 | MeOH | 81 |
16 | 10 | 1 + Et3N | 30 | MeOH | 81 |
17 | 10 | 1 + Et3N | 20 | iPrOH | 79 |
18 | 10 | 1 + Et3N | 20 | EtOH | 76 |
19 | 10 | 1 + Et3N | 20 | THF | 71 |
20 | 10 | 1 + Et3N | 20 | CH2Cl2 | 62 |
21 | 10 | 1 + Et3N | 20 | Toluene | 66 |
Entry | Compound | R | Yield (%) |
---|---|---|---|
1 | 3 | H | 81 |
2 | 4 | p-Me | 72 |
3 | 5 | o-Me | 77 |
4 | 6 | p-Cl | 90 |
5 | 7 | o-Cl | 87 |
6 | 8 | m-Cl | 83 |
7 | 9 | p-Br | 85 |
8 | 10 | m-Br | 82 |
9 | 11 | p-MeO | 66 |
10 | 12 | o-MeO | 58 |
11 | 13 | p-NO2 | 93 |
12 | 14 | m-NO2 | 88 |
Complex | 1 | 2 |
---|---|---|
Formula | C22H33N3NiO7 | C22H31N3O6Zn |
Fw | 510.22 | 498.87 |
Crystal system | Monoclinic | Monoclinic |
Space group | P21/n | C2/c |
a (Å) | 8.687 (5) | 16.798 (4) |
b (Å) | 15.248 (8) | 6.5119 (17) |
c (Å) | 20.858 (11) | 22.933 (6) |
α (◦) | 90 | 90 |
β (◦) | 93.384 (10) | 106.792 (9) |
γ (◦) | 90 | 90 |
Volume (Å3) | 2758 (3) | 2401.6 (11) |
Z | 4 | 4 |
Dcalcd/(g·cm−3) | 1.229 | 1.38 |
θ range (◦) | 1.7–27.3 | 2.7–27.4 |
μ (mm−1) | 0.744 | 1.064 |
F (000) | 1080 | 1048 |
Crystal size (mm) | 0.12 × 0.13 × 0.14 | 0.22 × 0.24 × 0.26 |
Reflections collected | 15,493 | 10,092 |
Unique reflections (Rint) | 5971 (0.050) | 2740 (0.042) |
Goodness-of-fit on F2 | 1.014 | 1.031 |
Final R indices [I > 2σ(I)] | R1 = 0.0509, wR2 = 0.1195 | R1 = 0.0376, wR2 = 0.0890 |
R indices (all data) | R1 = 0.0936,wR2 = 0.1351 | R1 = 0.0500, wR2 = 0.0945 |
Largest diff. peak and hole (e Å−3) | 0.55 and −0.38 | 0.29 and −0.35 |
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Liu, C.; Yang, Z.; Guo, H.; Zhao, Y.-C. Synthesis and Catalytic Application of Two Mononuclear Complexes Bearing Diethylenetriamine Derivative Ligand. Molecules 2020, 25, 2101. https://doi.org/10.3390/molecules25092101
Liu C, Yang Z, Guo H, Zhao Y-C. Synthesis and Catalytic Application of Two Mononuclear Complexes Bearing Diethylenetriamine Derivative Ligand. Molecules. 2020; 25(9):2101. https://doi.org/10.3390/molecules25092101
Chicago/Turabian StyleLiu, Chao, Zhao Yang, Hao Guo, and Yu-Cai Zhao. 2020. "Synthesis and Catalytic Application of Two Mononuclear Complexes Bearing Diethylenetriamine Derivative Ligand" Molecules 25, no. 9: 2101. https://doi.org/10.3390/molecules25092101