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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 dimers

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Abstract

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.

Graphical abstract: 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 dimers

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Publication details

The article was received on 04 Aug 2017, accepted on 25 Sep 2017 and first published on 25 Sep 2017


Article type: Paper
DOI: 10.1039/C7DT02878D
Citation: Dalton Trans., 2017, Advance Article
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    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 dimers

    D. V. Konarev, S. S. Khasanov, A. F. Shestakov, A. M. Fatalov, M. S. Batov, A. Otsuka, H. Yamochi, H. Kitagawa and R. N. Lyubovskaya, Dalton Trans., 2017, Advance Article , DOI: 10.1039/C7DT02878D

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