Cis-thioindigo (TI) – a new ligand with accessible radical anion and dianion states. Strong magnetic coupling in the {[TI-(μ2-O),(μ-O)]Cp*Cr}2 dimersстатья
Статья опубликована в высокорейтинговом журнале
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Дата последнего поиска статьи во внешних источниках: 23 ноября 2017 г.
Аннотация:Reaction of decamethylchromocene (Cp*2Cr) with thioindigo (TI) yields a coordination complex {[TI-(μ2-O), (μ-O)]Cp*Cr}2·C6H14 (1) in which one Cp* ligand in Cp*2Cr is substituted by TI. TI adopts cis-conformation in 1 allowing the coordination of both carbonyl groups to chromium. Additionally, one oxygen atom of TI becomes a μ2-bridge for two chromium atoms to form {[TI-(μ2-O), (μ-O)]Cp*Cr}2 dimers with a Cr⋯Cr distance of 3.12 Å. According to magnetic data, diamagnetic TI2− dianions and two Cr3+ atoms with a high S = 3/2 spin state are present in a dimer allowing strong antiferromagnetic coupling between two Cr3+ spins with an exchange interaction of −35.4 K and the decrease of molar magnetic susceptibility below 140 K. Paramagnetic TI˙− radical anions with the S = 1/2 spin state have also been obtained and studied in crystalline {cryptand[2,2,2](Na+)}(TI˙−) (2) salt showing that both radical anion and dianion states are accessible for TI.