Compound 33: Tetrakis((4-(ethoxycarbonyl)-1-(4-methoxybenzyl)-1H-pyrazol-5-yl)oxy)zirconium

DOI: 10.14469/hpc/11372 Metadata

Created: 2022-10-11 14:07

Last modified: 2024-07-03 13:47

Author: Henry Rzepa

License: Creative Commons: Public Domain Dedication 1.0

Funding: (none given)

Description

1H and 13C primary NMR, IR and crystal data for Tetrakis((4-(ethoxycarbonyl)-1-(4-methoxybenzyl)-1H-pyrazol-5-yl)oxy)zirconium (33): ZrCl4•2THF (52.0 mg, 0.138 mmol, 1.00 equiv) was added with stirring pyrazolone 8 (153 mg, 0.554 mmol, 4.00 equiv) in EtOH (3.0 mL) at 79 °C. The mixture was heated at reflux for 14 h, cooled to room temperature, and the precipitate was collected by filtration and dried in vacuo. Zr-pyrazolone complex 33 (76.0 mg, 0.0637 mmol, 46%) was obtained as a white solid, essentially pure by its 1H NMR spectrum. Crystals suitable for X-ray crystallography were obtained by slow evaporation from an EtOH solution of complex 33. 1H-NMR (400 MHz, OC(CD3)2): δ (ppm) = 7.48 (s, 1H), 7.30 – 7.20 (m, 2H), 6.75 – 6.67 (m, 2H), 4.92 (s, 2H), 3.74 (t, J = 7.1 Hz, 2H), 3.69 (s, 2H), 0.98 (t, J = 7.1 Hz, 3H). 1H-NMR (400 MHz, CDCl3): δ (ppm) = 7.53 (s, 1H), 7.23 – 7.20 (m, 2H), 6.66 – 6.63 (m, 2H), 4.90 (s, 2H), 3.68 (s, 3H), 3.63 (q, J = 7.1 Hz, 2H), 0.98 (t, J = 7.1 Hz, 3H). 13C{1H}-NMR (101 MHz, OC(CD3)2): δ (ppm) = 168.6, 163.1, 160.1, 137.2, 130.5, 130.4, 114.4, 94.6, 62.3, 55.5, 49.5, 14.5. 13C{1H}-NMR (101 MHz, CDCl3): δ (ppm) = 167.9, 162.2, 159.2, 137.4, 129.8, 129.3, 113.9, 94.1, 61.7, 55.3, 49.1, 14.2. IR (Diamond-ATR, neat) νmax (cm-1) = 1607, 1535, 1511, 1438, 1424, 1385, 1354, 1318, 1245, 1222, 1194, 1174, 1088, 1030, 805, 783, 760 742. HRMS (ES-ToF) m/z: [M + H]+ calc. for (C56H61N8O16Zr)+: 1191.3247, found: 1191.3220. m.p.: 150 – 152 °C (EtOH). Anal. Calcd for C56H60N8O16Zr ∙ C6H14: C, 58.24; H, 5.83; N, 8.76. Found: C, 58.64; H, 5.70; N, 8.43.

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DOIDescription
10.14469/hpc/10386 Syntheses and Characterization of Main Group, Transition Metal, Lanthanide and Actinide Complexes of Bidentate Acylpyrazolone Ligands

Members

DOIDescription
10.14469/hpc/11615 NMR Data for Compound 33.
10.14469/hpc/11614 IR Data for Compound 33.
10.14469/hpc/11388 Primary crystal structure data for Compound 33. Tetrakis((4-(ethoxycarbonyl)-1-(4-methoxybenzyl)-1H-pyrazol-5-yl)oxy)zirconium

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