Oxidation of [(Ar^BIG-bian)²⁻Yb²⁺(dme)] (1) (Ar^BIG-bian = 1,2-bis[(2,6-dibenzhydryl-4-methylphenyl)imino]acenaphthene; dme = 1,2-dimethoxyethane) by 0.5 equivalent of Me₂NC(S)S–S(S)CNMe₂ in dme at ambient temperature affords a mixture of two products, [(Ar^BIG-bian)²⁻Yb³⁺{SC(S)NMe₂}¹⁻(dme)] and [(Ar^BIG-bian)¹⁻Yb²⁺{SC(S)NMe₂}¹⁻(dme)], which represent two redox-isomers (2a and 2b, respectively). Their ratio in solution depends on the solvent as well as on the temperature. In the solid state, a decrease of temperature (350 → 100 K) caused an electron transfer from the Yb²⁺ ion to the Ar^BIG-bian radical-anion in isomer 2b to afford isomer 2a. Accordingly, the ratio of isomers 2a and 2b changes from 1 : 1 (350 K) to 3 : 1 (100 K). In contrast, in the dimer [(dme)(dpp-bian)¹⁻Yb²⁺(μ-Cl)₂Yb³⁺(dpp-bian)²⁻(dme)] (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene), which is the sole example of a lanthanide complex that reveals solid-state redox-isomerism (valence tautomerism) reported so far, the electron transfer from the Yb²⁺ ion to the dpp-bian radical-anion takes place at around 150 K and is completed within a temperature interval of ca. 7 K.

中文翻译：

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镧系元素的逐渐固态氧化还原异构现象

[(Ar ^BIG -bian) ²⁻ Yb ²⁺ (dme)] ( 1 ) (Ar ^BIG -bian = 1,2-双[(2,6-二二苯甲基-4-甲基苯基)亚氨基]苊的氧化；dme = 1,2-二甲氧基乙烷）与 0.5 当量的 Me ₂ NC(S)S–S(S)CNMe ₂在二甲醚中在环境温度下反应得到两种产物的混合物，[(Ar ^BIG -bian) ²⁻ Yb ³⁺ {SC (S)NMe ₂ } ¹⁻ (dme)] 和 [(Ar ^BIG -bian) ¹⁻ Yb ²⁺ {SC(S)NMe ₂ } ¹⁻ (dme)]，代表两种氧化还原异构体（2a和2b ） ， 分别）。它们在溶液中的比例取决于溶剂以及温度。在固态下，温度降低(350 → 100 K)导致电子从Yb ²⁺离子转移到异构体2b中的Ar ^BIG -bian自由基阴离子，得到异构体2a。因此，异构体2a和2b的比例从1:1(350K)变为3:1(100K)。相反，在二聚体中 [(dme)(dpp-bian) ¹⁻ Yb ²⁺ (μ-Cl) ₂ Yb ³⁺ (dpp-bian) ²⁻ (dme)] (dpp-bian = 1,2-bis [(2,6-二异丙基苯基)亚氨基]苊），这是迄今为止报道的揭示固态氧化还原异构（化合价互变异构）的稀土配合物的唯一例子，电子从Yb ²⁺离子转移到dpp -bian 自由基-阴离子在 150 K 左右发生，并在ca的温度区间内完成。 7K。