DOI: 10.14469/hpc/11374 Metadata

Created: 2022-10-11 14:11

Last modified: 2024-06-27 16:47

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 Cyclopentadienyl-bis((4-(ethoxycarbonyl)-1-(4-methoxybenzyl)-1H-pyrazol-5-yl)oxy)zirconium chloride (37): Cp2ZrCl2 (147 mg, 0.501 mmol, 1.00 equiv) was added with stirring to pyrazolone 8 (277 mg, 1.00 mmol, 2.00 equiv) and pyridine (79.0 mg, 0.08 mL, 1.00 mmol, 2.00 equiv) in THF (10 mL) at 65 °C. The mixture was heated at reflux for 16 h, was cooled to room temperature, diluted with CH2Cl2 (10 mL) and a mixture of Et2O and hexanes (1 : 1; 30 mL) was added. The precipitated pyridine hydrochloride was removed by filtration and the filtrate was evaporated. Recrystallization of the residue from PhMe and hexanes gave Zr-pyrazolone complex 37 (214 mg, 0.288 mmol, 57%) as a white solid. 1H-NMR (400 MHz, CDCl3): δ (ppm) = 7.56 (s, 1H), 7.48 (s, 1H), 7.45 (d, J = 3.2 Hz, 1H), 7.42 – 7.37 (m, 2H), 7.31 – 7.26 (m, 5H), 6.93 – 6.89 (m, 1H), 6.87 (dd, J = 8.7, 3.3 Hz, 2H), 6.84 – 6.80 (m, 2H), 6.60 – 6.53 (m, 1H), 6.50 (s, 5H), 6.49 (s, 4H), 5.17 – 5.02 (m, 3H), 5.02 – 4.95 (m, 1H), 4.87 – 4.78 (m, 2H), 4.69 (d, J = 14.7 Hz, 1H), 4.47 (dq, J = 10.8, 7.1 Hz, 1H), 4.35 (dq, J = 10.9, 7.1 Hz, 1H), 3.87 (dqd, J = 10.8, 7.1, 2.0 Hz, 2H), 3.80 (s, 3H), 3.77 – 3.69 (m, 8H), 3.38 (dq, J = 10.9, 7.1 Hz, 1H), 3.17 (dq, J = 10.9, 7.1 Hz, 1H), 1.40 (t, J = 7.1 Hz, 2H), 1.04 (t, J = 7.1 Hz, 3H), 0.96 (t, J = 7.1 Hz, 2H), 0.78 (t, J = 7.2 Hz, 3H). 13C{1H}-NMR (101 MHz, CDCl3): δ (ppm) = 169.5, 169.1, 168.1, 168.0, 162.1, 161.7, 161.4, 161.2, 159.4, 159.3, 159.1, 137.8, 137.6, 137.5, 137.4, 130.6, 129.2, 129.1, 129.1, 128.9, 128.7, 128.6, 118.2, 118.0, 114.2, 114.0, 114.0, 113.9, 94.5, 93.9, 93.1, 93.0, 63.6, 62.6, 62.2, 62.2, 55.4, 55.3, 55.2, 49.6, 49.6, 49.4, 49.1, 14.6, 14.1, 13.9. IR (Diamond-ATR, neat) νmax (cm-1) = 1593, 1532, 1511, 1443, 1384, 1353, 1327, 1228, 1176, 1088, 1028, 798, 775. HRMS (APCI) m/z: [M + H]+ calc. for (C33H36ClN4O8Zr)+: 741.1263, found: 741.1297. m.p.: 173 – 175 °C (PhMe/hexanes). Anal. Calcd for C33H35ClN4O8Zr ∙ 0.2 C7H8: C, 54.31; H, 4.85; N, 7.36. Found: C, 54.30; H, 4.86; N, 7.36.

Member of collection / collaboration

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

Members

DOI	Description
10.14469/hpc/11610	IR Data for Compound 37.
10.14469/hpc/11611	NMR Data for Compound 37.
10.14469/hpc/11391	Primary crystal structure data for Compound 37

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