Nizovtsev A, Scheurer A, Kosog B, Heinemann FW, Meyer K (2013)
Publication Type: Journal article, Original article
Publication year: 2013
Original Authors: Nizovtsev A.V., Scheurer A., Kosog B., Heinemann F.W., Meyer K.
Publisher: Wiley-VCH Verlag
Pages Range: 2538-2548
Journal Issue: 14
Starting from phenols ArOH (5) and the anisole derivative 3,5-di-tert-butyl-2-methoxybenzyl bromide (13), a series of new tacn-based ligands (ArOR)tacn (2) have been synthesized with substituents of varying bulkiness and electronic nature at the ortho and para positions with respect to the oxygen coordination site. It was observed that these groups not only determine the steric shielding and solubility properties of 2, but also deactivate the reactivity of the phenols in the modified Mannich reaction when electron-withdrawing groups are introduced at the para position in 5. Treatment of the ligands with UCl in thf led to the isolation of four uranium(IV) chloro complexes [{( ArO)tacn}UCl] (14), which were characterized by different spectroscopic and physical methods (e.g., H NMR, UV/Vis, SQUID), corroborating the +4 oxidation state in 14. Single-crystal X-ray structure analyses revealed that 14a·CH Cl·CHCN and 14b·1.25CH Cl crystallize in the chiral, orthorhombic space group P222 [a = 24.934(3), b = 27.941(3), c = 9.045(1) Å, V = 6302(2) Å, Z = 4] and the chiral, hexagonal space group P6 [a = 22.097(3), c = 17.941(2) Å, V = 7587(2) Å, Z = 4], respectively. Interestingly, complexes 14a,b self-organize in the solid state into homochiral 1D polymeric superstructures as a result of weak intermolecular C-H⋯Cl contacts. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
APA:
Nizovtsev, A., Scheurer, A., Kosog, B., Heinemann, F.W., & Meyer, K. (2013). Synthesis of differently substituted tacn-based ligands: Towards the control of solubility and electronic and steric properties of uranium coordination complexes. European Journal of Inorganic Chemistry, 14, 2538-2548. https://doi.org/10.1002/ejic.201201549
MLA:
Nizovtsev, Alexey, et al. "Synthesis of differently substituted tacn-based ligands: Towards the control of solubility and electronic and steric properties of uranium coordination complexes." European Journal of Inorganic Chemistry 14 (2013): 2538-2548.
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