N,N,N′,N′-tetrakis((1H-pyrazol-3-yl)methyl)-1,2-ethanediamine ligands as versatile scaffolds for second coordination sphere design
(2025) European Journal of Inorganic Chemistry — Vol. 28, n° 11, p. 1-10 (2025)
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EurJInorgChem-2025-Pochet-NNNNTetrakis1HPyrazol3Ylmethyl12EthanediamineLigandsasVersatile.pdf
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- The polypyrazole-containing ligands, N,N,N′,N′-tetrakis((5-tert-Butyl-1H-pyrazol-3-yl)methyl)-1,2-ethanediamine (L1) and N,N,N′,N′-tetrakis((5-Phenyl-1H-pyrazol-3-yl)methyl)-1,2-ethanediamine (L2) were synthesized and shown to form hexadentate monometallic coordination compounds with CoII, NiII, CuII and ZnII metal ions. Exchange studies with the metal ions show binding preference in the order of NiII>CoII/CuII>ZnII. The compounds were confirmed by NMR, UV-Vis studies and the X-ray crystals structures of [Co(L1)](PF6)2, [Ni(L1)](PF6)2, [Cu(L1)]ClPF6, [Zn(L1)](PF6)2, and [Ni(L2)]Cl2. In the solid state, the arrangement of the bulky pyrazole units leads to the formation of two distinct cationic pockets containing the N−H groups of the pyrazoles. These cationic pockets are found to bind Cl− or PF6− counterions through hydrogen bonding and anions titrations revealed good affinity for Cl− and Br−. The compounds can be dehydronated up to two times using mild organic bases, highlighting the potential of these ligands to tune the electronic properties of the metal center.
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Pochet, C., Laurent, T., Wang, M., Rotaru, A., Robeyns, K., Garcia, Y., & Singleton, M. (2025). N,N,N′,N′-tetrakis((1H-pyrazol-3-yl)methyl)-1,2-ethanediamine ligands as versatile scaffolds for second coordination sphere design. European Journal of Inorganic Chemistry, 28(11), 1-10. https://doi.org/10.1002/ejic.202400835 (Original work published 2025)