2026-10-15T08:42:04Z https://api.figshare.com/v2/oai

oai:figshare.com:article/31748533 2026-06-18T11:57:28Z category_25111 category_25129 category_25135 category_25234 category_25108 portal_918 item_type_3 month_year_06_2026

One- and Two-Electron Reduction of N-Heterocycles by Divalent Rare Earth Terphenyl Anilide Complexes Conrad Goodwin (11850479) Ross MacKenzie (17988429) Benjamin Réant (21743296) George F. S. Whitehead (5732672) Eric J. L. McInnes (5732655) Iain Cameron (23124359) Harry Silver (23546517) F-block chemistry Organometallic chemistry Transition metal chemistry Electrochemistry Crystallography Yttrium Lanthanum Lutetium Divalent Reduction <p dir="ltr">Supporting research data for: One-and Two-Electron Coordinatively-Induced Reduction of N-Heterocycles by Divalent Rare Earth Terphenyl Anilide Complexes</p><p dir="ltr">Abstract: Molecular rare-earth (RE) complexes in the divalent oxidation state have been used as potent one-electron reductants, yielding bonding motifs not accessible elsewhere in the periodic table. A deeper understanding of the chemical properties which dictate their reducing power is required to tame their reduction potentials and unlock new controlled reactivity. Here, we report the electrochemical characterisation of a series of divalent bis-(tethered)arene complexes, [M II (NHAr iPr6 )2] (1M, M = Y, La, Sm, Eu, Yb, Tm, Lu; NHAr iPr6 = {N(H)C6H3-2,6-(C6H2-2,4,6-iPr3)2}), and their reactivity towards the nitrogen heterocycles pyridine and 4,4′-bipyridine. Complexes 1Y, 1La, 1Tm, and 1Lu reduce 4,4′-bipyridine and reductively couple pyridine to afford the dimeric [{M III (NHAr iPr6 )2}2(µ-N2C10H8)] (2M, M = Y, La, Tm, Lu) and [{M III (NHAr iPr6 )2}2(µ-N2C10H10)] (3M, M = Y, La, Tm, Lu) respectively. These results contrast with electrochemical measurements, which place the RE(III/II) reduction potentials for all 1M complexes as insufficiently reducing for either heterocycle. These results imply the reactions proceed through coordination-induced reduction. Synthesis of 2M complexes also results in the formation of 4,4′-bipyridine radical species, which are probed by NMR, EPR, and UV-Vis-NIR spectroscopies.</p><p dir="ltr"><br></p> 2026-06-18T11:57:28Z Dataset Dataset 10.48420/31748533.v1 https://figshare.com/articles/dataset/One-_and_Two-Electron_Reduction_of_N-Heterocycles_by_Divalent_Rare_Earth_Terphenyl_Anilide_Complexes/31748533 CC BY 4.0