Compound 38: (m-O)-Di-[cyclopentadienyl-bis((4-(ethoxycarbonyl)-1-phenyl-1H-pyrazol-5-yl)oxy)zirconium]

Created: 2022-10-11 14:13

Last modified: 2024-11-22 09:38

License: Creative Commons: Public Domain Dedication 1.0

Funding: (none given)

Description

1H and 13C primary NMR, IR and crystal data for (m-O)-Di-[cyclopentadienyl-bis((4-(ethoxycarbonyl)-1-phenyl-1H-pyrazol-5-yl)oxy)zirconium] (38): Cp2ZrCl2 (148 mg, 0.506 mmol, 1.00 equiv) was added with stirring to pyrazolone 6 (235 mg, 1.01 mmol, 2.00 equiv) and pyridine (80.0 mg, 0.08 mL, 1.01 mmol, 2.00 equiv) in THF (10 mL) at 65 °C. The mixture was heated at reflux for 16 h, 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 38 (201 mg, 0.160 mmol, 32%) as a yellow-white solid. 1H-NMR (400 MHz, CDCl3): δ (ppm) = 7.96 – 7.86 (m, 5H), 7.80 (s, 1H), 7.78 (s, 1H), 7.71 (s, 1H), 7.65 (s, 1H), 7.57 (s, 2H), 7.57 – 7.52 (m, 1H), 7.48 (t, J = 7.8 Hz, 2H), 7.37 (q, J = 7.5 Hz, 2H), 7.28 (dd, J = 8.8, 6.7 Hz, 3H), 7.18 (t, J = 7.5 Hz, 1H), 6.60 (d, J = 1.8 Hz, 8H), 4.51 (ddq, J = 57.2, 10.8, 7.1 Hz, 1H), 4.22 (dq, J = 10.9, 7.2 Hz, 1H), 4.13 (dq, J = 10.8, 7.2 Hz, 1H), 3.95 (dq, J = 10.6, 7.1 Hz, 2H), 3.78 (dq, J = 10.6, 7.1 Hz, 1H), 1.49 (t, J = 7.1 Hz, 2H), 1.26 (t, J = 7.2 Hz, 3H), 1.20 (t, J = 7.1 Hz, 2H), 1.11 (t, J = 7.0 Hz, 3H). 13C{1H}-NMR (101 MHz, CDCl3): δ (ppm) = 169.7, 169.4, 168.6, 168.3, 162.2, 162.0, 161.5, 161.1, 138.9, 138.8, 138.7, 138.6, 138.4, 138.3, 138.2, 129.2, 129.2, 129.1, 129.0, 128.7, 126.8, 126.6, 126.4, 126.2, 121.8, 121.4, 120.9, 120.5, 120.2, 118.3, 118.1, 95.5, 95.1, 94.3, 93.9, 63.9, 63.1, 62.9, 62.6, 14.7, 14.2, 14.2. IR (Diamond-ATR, neat) νmax (cm-1) = 1651, 1634, 1612, 1593, 1586, 1541, 1530, 1500, 1489, 1467, 1431, 1387, 1357, 1321, 1254, 1117, 1084, 1055, 1009, 954, 775, 738, 690. HRMS (ES-ToF) m/z: [M + H]+ calc. for ()+:, found:. m.p.: >190 °C (decomp.). Anal. Calcd for C58H54N8O13Zr2 ∙ 0.35 ZrO2: C, 53.07; H, 4.15; N, 8.54. Found: C, 53.50; H, 4.10; N, 8.32.

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/11612	IR Data for Compound 38.
10.14469/hpc/11613	NMR Data for Compound 38.
10.14469/hpc/11392	Primary crystal structure data for Compound 38. (m-O)-Di-[cyclopentadienyl-bis((4-(ethoxycarbonyl)-1-phenyl-1H-pyrazol-5-yl)oxy)zirconium]

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