| ¹H NMR (500 MHz, CDCl₃) | δ 11.17 (s, 1H, CHO), 9.85 (s, 1H, OH), 7.39 (s, 1H, ArH), 7.28 (s, 1H, ArH), 4.72 (s, 2H, ArCH₂OH), 2.37 (br, 1H, OH), 2.33 (s, 3H, CH₃); image data were not transcribed |
|---|
Hieu D. Nguyen, Lorenzo C. Ruiz De Castilla, Muhammad Usama Gul Khan, Hoang T. Dang, Tuhin Ganguly, Judy I. Wu, Mohamed Elanany, Loi H. Do. “Ethylene to medium-chain linear alpha olefins: alkali cation modulation of nickel oligomerization selectivity.” ChemRxiv (). https://doi.org/10.26434/chemrxiv.15007822/v1
A terminal conversion outcome was not retained
| ¹H NMR (500 MHz, CDCl₃) | δ 7.14 (s, 2H, ArH), 4.17 – 4.09 (m, 4H, 2×OCH₂), 3.73 – 3.66 (m, 2H, OCH₂), 3.58 – 3.53 (m, 6H, 3×OCH₂), 3.48 – 3.46 (m, 2H, 2×CHCH₃), 3.31 (s, 3H, OCH₃), 2.86 (hept, J = 6.9 Hz, 1H, CHCH₃), 1.21 (m, 18H, 3×(CHCH₃)₂); image data were not transcribed |
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| ¹H NMR (500 MHz, CDCl₃) | δ 11.01 (s, 1H, CHO), 9.81 (s, 1H, OH), 7.45 (s, 1H, ArH), 7.23 (s, 1H, ArH), 4.58 (s, 2H, ArCH₂), 3.70 – 3.60 (m, 10H, 5×OCH₂), 3.53 – 3.49 (m, 2H, OCH₂), 3.33 (s, 3H, OCH₃), 2.29 (s, 3H, ArCH₃); image data were not transcribed |
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| ¹³C NMR (126 MHz, CDCl₃) | δ 196.67, 157.19, 137.37, 132.64, 128.96, 126.73, 120.10, 72.00, 70.71, 70.70, 70.63, 70.62, 70.11, 66.82, 59.12, 20.41; image data were not transcribed |
| ¹H NMR (500 MHz, CDCl₃) | δ 8.56 (d, J = 1.3 Hz, 1H, HC=N), 7.40 (td, J = 8.0, 7.6, 1.4 Hz, 2H, ArH), 7.32 (d, J = 2.0 Hz, 1H, ArH), 7.28 – 7.24 (m, 3H, ArH), 7.11 (d, J = 2.0 Hz, 1H, ArH), 4.67 (s, 2H, ArCH₂), 3.76 – 3.61 (m, 10H, 5×OCH₂), 3.54 – 3.52 (m, 2H, OCH₂), 3.36 (s, 3H, OCH₃), 2.31 (s, 3H, ArCH₃); image data were not transcribed |
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| ¹³C NMR (126 MHz, CDCl₃) | δ 162.75, 156.89, 148.55, 133.82, 131.70, 129.51 (2C), 127.91, 126.93, 126.10, 121.22 (2C), 118.53, 72.04, 70.75, 70.73, 70.71, 70.64, 69.95, 67.51, 59.15, 20.54; image data were not transcribed |
| ESI-MS(+) | Calc. for C₂₂H₂₉NO₅ [M+H]⁺ = 388.2124, found 388.2124; image data were not transcribed |
| ¹H NMR (400 MHz, benzene-d₆) | δ 7.94 (d, J = 8.5 Hz, 1H, HC=N), 7.70 – 7.62 (m, 7H, ArH), 7.11 – 7.06 (m, 2H, ArH), 7.02 – 6.98 (m, 3H, ArH), 6.94 – 6.90 (m, 6H, ArH), 6.80 – 6.77 (m, 2H, ArH), 6.73 – 6.70 (m, 3H, ArH), 6.61 – 6.59 (m, 1H, ArH), 6.40 (t, J = 7.1 Hz, 1H), 6.31 (t, J = 7.3 Hz, 2H), 3.65 (s, 2H, ArCH₂), 3.53 – 3.43 (m, 8H, 4×OCH₂), 3.37 – 3.34 (m, 2H, OCH₂), 3.31 – 3.28 (m, 2H, OCH₂), 3.12 (s, 3H, OCH₃), 2.17 (s, 3H, ArCH₃); image data were not transcribed |
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| ³¹P NMR (162 MHz, benzene-d₆) | δ 28.59; image data were not transcribed |
| ESI-MS | The molecular ion of Ni3 was not detected, even under very mild ionization conditions; dominant ions were ligand-derived fragments [4a+H]⁺ (m/z = 388.2) and [4a+Na]⁺ (m/z = 410.2); additional assignable ions were [PPh₃+C₆H₅]⁺ (m/z = 339.1), [oxidized 4a+Na]⁺ (m/z = 426.2), [4a+Ni]⁺ (m/z = 446.3), [4a+Ni+Na]⁺ (m/z = 468.3), and [4a+Ni+C₆H₅]⁺ (m/z = 649.9), where 4a = C₂₂H₂₉NO₅; image data were not transcribed |
| IR, ṽ (cm⁻¹) | 496.6, 690.2, 854.5, 1023.1, 1102.8, 1185.2, 1250.6, 1439.9, 1541.6, 1591.6, 2878.7 |
| ¹H NMR and LC–MS | Product-to-impurity ratio approximately 65:35; impurity mostly aldehyde starting material |
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| ¹H NMR and LC–MS | Product-to-impurity ratio approximately 55:45; impurity mostly aldehyde starting material |
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| ¹H NMR (500 MHz, CDCl₃) | δ 8.24 (br, 1H, HC=N), 7.21 (s, 1H, ArH), 6.95 (s, 1H, ArH), 4.62 (s, 2H, ArCH₂), 3.72 – 3.60 (m, 10H, 5×OCH₂), 3.55 – 3.49 (m, 2H, OCH₂), 3.35 (s, 3H, OCH₃), 2.25 (s, 3H, ArCH₃), 2.17 – 2.12 (m, 3H, 3×CH), 1.82 – 1.78 (m, 6H, 3×CH₂), 1.75 – 1.63 (m, 6H, 3×CH₂); image data were not transcribed |
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| ¹³C NMR (126 MHz, CDCl₃) | δ 171.09, 159.27, 132.65, 130.72, 126.34, 126.12, 117.87, 71.95, 70.63, 70.61, 70.54, 69.78, 67.60, 60.37, 59.00, 56.94, 42.99, 36.29, 29.37, 21.02, 20.42, 14.20; image data were not transcribed |
| ESI-MS(+) | Calc. for C₂₆H₃₉NO₅ [M+H]⁺ = 446.2906, found 446.2905; image data were not transcribed |
| ¹H and ¹³C NMR after standing overnight | Trace amounts of aldehyde starting material were detected (~10 %) |
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| ¹H NMR (500 MHz, CDCl₃) | δ 8.46 (s, 1H, HC=N), 7.41 (td, J = 7.7, 1.9 Hz, 1H, ArH), 7.38 – 7.31 (m, 3H, ArH), 7.26 – 7.24 (m, 1H, ArH), 7.22 (dd, J = 7.4, 1.7 Hz, 1H, ArH), 7.17 (d, J = 8.0 Hz, 2H, ArH), 7.04 – 6.97 (m, 2H, ArH + OH), 6.92 (d, J = 8.3 Hz, 1H, ArH), 4.57 (s, 2H, ArCH₂), 3.71 – 3.64 (m, 13H, 5×OCH₂ + ArOCH₃), 3.59 – 3.51 (m, 2H, OCH₂), 3.37 (s, 3H, OCH₃), 2.28 (s, 3H, ArCH₃); image data were not transcribed |
| ¹³C NMR (126 MHz, CDCl₃) | δ 162.58, 156.59, 147.59, 133.90, 133.23, 131.39, 131.33, 131.24, 129.21, 128.68, 128.49, 128.36, 127.51, 126.65, 126.07, 120.59, 118.63, 118.37, 110.86, 72.05, 70.77, 70.73, 70.72, 70.66, 69.90, 67.23, 59.16, 55.40, 20.53; image data were not transcribed |
| ESI-MS(+) | Calc. for C₂₉H₃₅NO₆ [M+H]⁺ = 494.2543, found 494.2535; image data were not transcribed |
| ¹H NMR (500 MHz, CDCl₃) | δ 8.36 (s, 1H, HC=N), 7.38 – 7.23 (m, 6H, ArH), 7.18 (td, J = 7.4, 1.2 Hz, 1H, ArH), 7.10 – 7.04 (m, 3H, ArH), 6.97 – 6.93 (m, 2H, ArH), 6.88 (tt, J = 7.2, 1.1 Hz, 1H, ArH), 6.77 – 6.74 (m, 2H, ArH), 4.59 (s, 2H, ArCH₂), 3.74 – 3.62 (m, 10H, 5×OCH₂), 3.57 – 3.51 (m, 2H, OCH₂), 3.36 (s, 3H, OCH₃), 2.28 (s, 3H, ArCH₃); image data were not transcribed |
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| ¹³C NMR (126 MHz, CDCl₃) | δ 163.08, 157.33, 156.57, 154.35, 147.59, 137.94, 133.36, 133.19, 131.99, 131.61, 131.44, 131.29, 129.50, 129.22, 128.98, 128.42, 127.62, 126.54, 126.16, 125.51, 123.63, 122.77, 119.21, 118.79, 118.50, 72.10, 70.82, 70.80, 70.77, 70.70, 70.02, 67.33, 59.16, 20.57; image data were not transcribed |
| ESI-MS(+) | Calc. for C₃₄H₃₇NO₆ [M+H]⁺ = 556.2699, found 556.2707; image data were not transcribed |
| ¹H NMR (400 MHz, CDCl₃) | δ 7.35 (s, 2H, HC=N), 7.25 (d, J = 4.4 Hz, 2H, ArH), 7.12 (d, J = 7.6 Hz, 4H, ArH), 6.96 (dd, J = 7.9, 1.9 Hz, 2H, ArH), 6.89 (ddd, J = 8.7, 6.9, 1.8 Hz, 2H, ArH), 6.44 – 6.27 (m, 2H, ArH), 5.56 (d, J = 8.3 Hz, 2H, ArH), 4.23 (hept, J = 6.9 Hz, 4H, 4×CH(CH₃)₂), 1.44 (d, J = 6.9 Hz, 12H, 2×CH(CH₃)₂), 1.21 (d, J = 6.9 Hz, 12H, 2×CH(CH₃)₂); image data were not transcribed |
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| ESI-MS(+) | Calc. for expected molecular ion C₃₈H₄₄N₂O₂Ni = 618.2756, found [M+H]⁺ = 619.2837; image data were not transcribed |
| ¹H NMR (400 MHz, CDCl₃) | δ 7.88 (d, J = 8.3 Hz, 2H, ArH), 7.50 – 7.44 (m, 4H, ArH), 7.36 (dd, J = 8.3, 7.3 Hz, 2H, ArH), 7.27 – 7.23 (m, 2H, ArH), 7.15 – 7.10 (m, 4H, ArH), 6.82 (d, J = 7.3 Hz, 2H, ArH); image data were not transcribed |
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| ¹H NMR (400 MHz, CDCl₃) | δ 7.17 – 7.15 (m, 4H, ArH), 6.70 – 6.68 (m, 4H, ArH), 2.34 (s, 6H, 2Ar–CH₃), 2.14 (s, 6H, 2CH₃); image data were not transcribed |
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| ESI-MS(+) | Calc. for expected molecular ion C₂₄H₁₆Br₂N₂Ni = 547.9034, found [Ni5−Br]⁺ = 468.3; other dominant assignable ligand-derived ions were [ligand+H]⁺ (m/z = 333.1) and [ligand+Br]⁺ (m/z = 410.2), where ligand = C₂₄H₁₆N₂; image data were not transcribed |
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| ESI-MS(+) | Calc. for expected molecular ion C₁₈H₂₀Br₂N₂Ni = 479.9347, found [C₁₈H₂₀N₂+H]⁺ (ligand+H ion; m/z = 265.2), [2C₁₈H₂₀N₂+Ni+Br]⁺ (m/z = 667.2), [C₃₆H₄₂N₄Ni₂Br₂] (Ni6 dimer, m/z = 804.04, found 803.1); image data were not transcribed |
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| ¹H NMR (500 MHz, CDCl₃) | δ 8.51 (br, 1H, NH), 8.24 (dd, J = 7.9, 1.9 Hz, 1H, ArH), 7.51 – 7.47 (m, 4H, ArH), 7.45 – 7.42 (m, 1H, ArH), 7.38 – 7.33 (m, 6H, ArH), 7.06 (t, J = 7.6, 1H, ArH), 6.92 (d, J = 8.4, 1H, ArH), 4.07 (q, J = 7.0 Hz, 2H, OCH₂CH₃), 1.10 (t, J = 7.0 Hz, 3H, CH₃); image data were not transcribed |
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| ¹³C NMR (126 MHz, CDCl₃) | δ 168.03 (CONH), 157.47 (ArCOEt), 138.82 (d, ²JC–P = 13.9 Hz), 133.56, 132.93, 131.83 (d, ¹JC–P = 29.0 Hz), 129.49, 128.66 (d, ³JC–P = 6.3 Hz), 121.37, 120.97, 112.18, 64.80 (OCH₂), 14.50 (CH₃); image data were not transcribed |
| ³¹P NMR (202 MHz, CDCl₃) | δ 23.14; image data were not transcribed |
| ESI-MS(+) | Calc. for C₂₁H₂₀NO₂P [M+H]⁺ = 350.1310, found 350.1312; image data were not transcribed |
| ³¹P NMR, crude reaction mixture | δ 76.2 |
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| ¹H NMR (500 MHz, benzene-d₆) | δ 8.70 (br, 1H), 8.51 (br, 1H), 8.31 – 8.20 (m, 2H), 7.32 – 7.07 (m, 4H), 7.16 – 6.27 (m, 11H), 3.70 (br, 2H, OCH₂), 1.27 – 1.16 (m, 3H, CH₃), 0.03 – −0.15 (m, 11H); image data were not transcribed |
| ³¹P NMR (202 MHz, benzene-d₆) | δ 76.18; image data were not transcribed |
| ³¹P NMR (202 MHz, CDCl₃) | Complete deprotonation; phosphorus resonance shifted from 4.52 to −10.73 ppm |
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| ³¹P NMR (202 MHz, benzene-d₆) | δ 17.92 (d, JP–P = 286.1 Hz), −0.01 (d, JP–P = 286.1 Hz, PPh₃); two phosphorus resonances corresponding to the coordinated phosphine ligand and PPh₃; coupling consistent with a trans relationship between the phosphorus centers and within the typical reported range for trans-phosphine coupling (200–400 Hz) |
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| UV–vis/BindFit analysis conditions | Ni8 (100 μM) in Et₂O; absorbance at 268 nm; quasi-Newtonian fitting method (L-BFGS-B); dilution correction; initial values subtracted; K initial guess = 100 M⁻¹ |
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| Preferred binding model | Data fit most satisfactorily to a 1:1 rather than 1:2 or 2:1 host–guest model regardless of the order of addition |
| Ni8/LiBArF₄ (1:1) + 15-crown-5 | 1:1 model: K = 100.00 M⁻¹ (±15.74 %); 2:1 model: K₁,₁ = 19519.23 M⁻¹ (±422.43 %), K₂,₁ = 17071.05 M⁻¹ (±230.55 %); 1:2 model: K₁,₁ = 10605.75 M⁻¹ (±33.00 %), K₁,₂ = 17317.45 M⁻¹ (±46.96 %) |
| Ni8 + LiBArF₄ | 1:1 model: K = 100.00 M⁻¹ (±4.06 %); 2:1 model: K₁,₁ = 1960.79 M⁻¹ (±11.24 %), K₂,₁ = 763.94 M⁻¹ (±5.24 %); 1:2 model: K₁,₁ = 2700.20 M⁻¹ (±11.55 %), K₁,₂ = 2950.70 M⁻¹ (±25.12 %) |
| Ni8/15-crown-5 (1:1) + LiBArF₄ | 1:1 model: K = 3355.79 M⁻¹ (±2.00 %); 2:1 model: K₁,₁ = 4841.45 M⁻¹ (±9.04 %), K₂,₁ = 1.16e−4 M⁻¹ (±194.95 %); 1:2 model: K₁,₁ = 375.56 M⁻¹ (±10.10 %), K₁,₂ = 43921.66 M⁻¹ (±72.19 %) |
| Ni8/NaBArF₄ (1:1) + 15-crown-5 | 1:1 model: K = 100.33 M⁻¹ (±10.15 %); 2:1 model: K₁,₁ = 1245.43 M⁻¹ (±63.46 %), K₂,₁ = 70414.14 M⁻¹ (±167.98 %); 1:2 model: K₁,₁ = 11187.49 M⁻¹ (±354.78 %), K₁,₂ = 183700.11 M⁻¹ (±608.07 %) |
| Ni8 + NaBArF₄ | 1:1 model: K = 95.26 M⁻¹ (±6.97 %); 2:1 model: K₁,₁ = 4547.09 M⁻¹ (±14.32 %), K₂,₁ = 46468.54 M⁻¹ (±11.22 %); 1:2 model: K₁,₁ = 4100.81 M⁻¹ (±231.37 %), K₁,₂ = 141194.56 M⁻¹ (±103.76 %) |
| Ni8/15-crown-5 (1:1) + NaBArF₄ | 1:1 model: K = 100.00 M⁻¹ (±2.81 %); 2:1 model: K₁,₁ = 122.40 M⁻¹ (±150.04 %), K₂,₁ = 40.95 M⁻¹ (±34.73 %); 1:2 model: K₁,₁ = 1000.00 M⁻¹ (±15.21 %), K₁,₂ = 100.00 M⁻¹ (±135.15 %) |
| Ni8/KBArF₄ (1:1) + 15-crown-5 | 1:1 model: K = 113.29 M⁻¹ (±15.23 %); 2:1 model: K₁,₁ = 1185.91 M⁻¹ (±130.68 %), K₂,₁ = 104953.24 M⁻¹ (±78.06 %); 1:2 model: K₁,₁ = 10014.49 M⁻¹ (±231.27 %), K₁,₂ = 676108.21 M⁻¹ (±274.25 %) |
| Ni8 + KBArF₄ | 1:1 model: K = 100.00 M⁻¹ (±4.08 %); 2:1 model: K₁,₁ = 9867.82 M⁻¹ (±13.51 %), K₂,₁ = 684.62 M⁻¹ (±9.49 %); 1:2 model: K₁,₁ = 8312.53 M⁻¹ (±47.61 %), K₁,₂ = 15812.70 M⁻¹ (±51.29 %) |
| Ni8/15-crown-5 (1:1) + KBArF₄ | 1:1 model: K = 100.04 M⁻¹ (±3.35 %); 2:1 model: K₁,₁ = 506.37 M⁻¹ (±10.40 %), K₂,₁ = 33538.41 M⁻¹ (±83.08 %); 1:2 model: K₁,₁ = 5213.07 M⁻¹ (±10.26 %), K₁,₂ = 0.10 M⁻¹ (±247.25 %) |
| Ni8/CsBArF₄ (1:1) + 15-crown-5 | 1:1 model: K = 100.00 M⁻¹ (±10.39 %); 2:1 model: K₁,₁ = 100.00 M⁻¹ (±38.53 %), K₂,₁ = 100.00 M⁻¹ (±0.49 %); 1:2 model: K₁,₁ = 1932.44 M⁻¹ (±27.82 %), K₁,₂ = 352.01 M⁻¹ (±77.32 %) |
| Ni8 + CsBArF₄ | 1:1 model: K = 100.00 M⁻¹ (±2.72 %); 2:1 model: K₁,₁ = 100.00 M⁻¹ (±42.60 %), K₂,₁ = 100.00 M⁻¹ (±3.02 %); 1:2 model: K₁,₁ = −2018.82 M⁻¹ (±−0.93 %), K₁,₂ = 810.22 M⁻¹ (±0.93 %)* |
| Ni8/15-crown-5 (1:1) + CsBArF₄ | 1:1 model: K = 100.04 M⁻¹ (±2.92 %); 2:1 model: K₁,₁ = 514.12 M⁻¹ (±15.43 %), K₂,₁ = 21690.95 M⁻¹ (±123.58 %); 1:2 model: K₁,₁ = 4028.06 M⁻¹ (±11.45 %), K₁,₂ = 5.67e−5 M⁻¹ (±198.09 %)* |
| BindFit reporting qualifier | Larger estimated K indicates a stronger interaction; negative or extremely large host–guest coefficient values indicate that the fitting model is not suitable; entries with large standard deviations for one or both K values were identified as problematic; source color highlighting of problematic entries was not transcribed |
| UV–vis (Ni8, 100 μM, Et₂O, RT; up to 1.0 equiv. LiBArF₄) | Isosbestic point at 282 nm, indicating conversion of Ni8 to a new species; image data were not transcribed |
| UV–vis (Ni8/15-crown-5, 100 μM, 1:1, Et₂O, RT; up to 1.0 equiv. LiBArF₄) | Isosbestic point at 282 nm, indicating conversion to a new species; image data were not transcribed |
| UV–vis (Ni8/LiBArF₄, 100 μM, 1:1, Et₂O, RT; up to 1.0 equiv. 15-crown-5) | Progressive decrease in absorbance, including a decrease in the absorbance band at 300 nm, without an observable isosbestic point; image data were not transcribed |
| UV–vis, final spectra from Ni8/15-crown-5 + LiBArF₄ and Ni8/LiBArF₄ + 15-crown-5 titrations | Highly similar features, indicating that the same Ni8/Li⁺/15-crown-5 species is likely present at equilibrium; image data were not transcribed |
| UV–vis (Ni8, 100 μM, Et₂O, RT; up to 1.0 equiv. NaBArF₄) | Isosbestic point at 282 nm, indicating conversion to a new species; image data were not transcribed |
| UV–vis (Ni8/15-crown-5, 100 μM, 1:1, Et₂O, RT; up to 1.0 equiv. NaBArF₄) | Isosbestic point at 282 nm, indicating conversion to a new species; image data were not transcribed |
| UV–vis (Ni8, 100 μM, Et₂O, RT; up to 1.0 equiv. KBArF₄) | Isosbestic point at 284 nm, indicating conversion to a new species; image data were not transcribed |
| UV–vis (Ni8/15-crown-5, 100 μM, 1:1, Et₂O, RT; up to 1.0 equiv. KBArF₄) | Isosbestic point at 284 nm, indicating conversion to a new species; image data were not transcribed |
| UV–vis (Ni8, 100 μM, Et₂O, RT; up to 1.0 equiv. CsBArF₄) | Isosbestic point at 282 nm, indicating conversion to a new species; image data were not transcribed |
| UV–vis (Ni8/15-crown-5, 100 μM, 1:1, Et₂O, RT; up to 1.0 equiv. CsBArF₄) | Isosbestic point at 282 nm, indicating conversion to a new species; image data were not transcribed |
| DLS conditions for 10 mM samples | Malvern Zetasizer Nano-ZS90; 25 °C; He-Ne laser, λ = 632.8 nm; scattering angle 173°; hydrodynamic diameters and polydispersity indices from cumulants analysis in accordance with ISO 13321:1996; size distributions calculated by intensity |
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| DLS (Ni8/Li⁺ and Ni8/Li⁺/15-crown-5, approximately 0.5 mM) | No large aggregates were detected |
| DLS (Ni8, 10 mM) | Averaged particle size 250 nm; image data were not transcribed |
| DLS (Ni8/15-crown-5, 10 mM, 1:1) | Averaged particle size 297 nm; image data were not transcribed |
| DLS (Ni8/LiBArF₄/15-crown-5, 10 mM, 1:1:1) | Averaged particle size 646 nm; image data were not transcribed |
| DLS (Ni8/LiBArF₄, 10 mM, 1:1) | Averaged particle size 794 nm; image data were not transcribed |