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Redox activity of a dissymmetric ligand bridging divalent ytter-bium and reactive nickel fragments

Abstract : The reaction of a reactive nickel dimethyl 1 bearing a redox-active, dissymmetric ligand, which is obtained by deprotonation of 2-pyrimidin-2-yl-1H-benzimidazole (Hbimpm) with a divalent lanthanide complex, Cp* 2 Yb(OEt 2), affords an unprecedented, trimeric 2 with C(sp 3)-C(sp 3) bond formation between two ligands in an exo position. Meanwhile, the transient, dimeric species 3 can be isolated with the same ligand coupling fashion, however, with a drastic distorsion angle of the bimpm ligand and reactive NiMe 2 fragment, revealing the possible mechanism of this rearrangement. A much more stable dimeric congener, 5, with an exo ligand coupling, is synthesized in the presence of 18-crown-6, which captures the potassium counter ion. The CC coupling formation between two bimpm ligands results from the effective electron transfer from divalent lanthanide fragments. Without the divalent lanthanide, the reductive coupling occurs on a different carbon of the ligand, nicely showing the modulation of the spin density induced by the presence of the lanthanide ion. The electronic structures of these complexes are investigated by magnetic study (SQUID), indicating a 2 F 7/2 ground state for each ytterbium in all the heterometallics. This work firstly reports ligand coupling reactivity in a redox-active, yet dissymmetric system with divalent organolanthanides, and the reactive nickel moiety can impact the intriguing transition towards a stable homoleptic, trinulear lanthanide species.
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Contributor : Grégory Nocton Connect in order to contact the contributor
Submitted on : Thursday, December 10, 2020 - 9:53:35 AM
Last modification on : Friday, December 11, 2020 - 3:53:46 AM
Long-term archiving on: : Thursday, March 11, 2021 - 6:50:14 PM


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Ding Wang, Maxime Tricoire, Valeriu Cemortan, Jules Moutet, Grégory Nocton. Redox activity of a dissymmetric ligand bridging divalent ytter-bium and reactive nickel fragments. Inorganic Chemistry Frontiers, Royal Society of Chemistry, 2020, ⟨10.1039/D0QI00952K⟩. ⟨hal-03050191⟩



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