Abstract
The redox interconversion between Co(III) thiolate and Co(II) disulfide compounds has been investigated experimentally and computationally. Reactions of cobalt(II) salts with disulfide ligand L1SSL1 (L1SSL1 = di-2-(bis(2-pyridylmethyl)amino)-ethyl disulfide) result in the formation of either the high-spin cobalt(II) disulfide compound [CoII 2(L1SSL1)Cl4] or a low-spin, octahedral cobalt(III) thiolate compound, such as [CoIII(L1S)(MeCN)2](BF4)2. Addition of thiocyanate anions to a solution containing the latter compound yielded crystals of [CoIII(L1S)(NCS)2]. The addition of chloride ions to a solution of [CoIII(L1S)(MeCN)2](BF4)2 in acetonitrile results in conversion of the cobalt(III) thiolate compound to the cobalt(II) disulfide compound [CoII 2(L1SSL1)Cl4], as monitored with UV-vis spectroscopy; subsequent addition of AgBF4 regenerates the Co(III) compound. Computational studies show that exchange by a chloride anion of the coordinated acetonitrile molecule or thiocyanate anion in compounds [CoIII(L1S)(MeCN)2]2+ and [CoIII(L1S)(NCS)2] induces a change in the character of the highest occupied molecular orbitals, showing a decrease of the contribution of the p orbital on sulfur and an increase of the d orbital on cobalt. As a comparison, the synthesis of iron compounds was undertaken. X-ray crystallography revealed that structure of the dinuclear iron(II) disulfide compound [FeII 2(L1SSL1)Cl4] is different from that of cobalt(II) compound [CoII 2(L1SSL1)Cl4]. In contrast to cobalt, reaction of ligand L1SSL1 with [Fe(MeCN)6](BF4)2 did not yield the expected Fe(III) thiolate compound. This work is an unprecedented example of redox interconversion between a high-spin Co(II) disulfide compound and a low-spin Co(III) thiolate compound triggered by the nature of the anion.
Original language | English |
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Pages (from-to) | 8796-8805 |
Number of pages | 10 |
Journal | Inorganic Chemistry |
Volume | 57 |
Issue number | 15 |
Early online date | 19 Jul 2018 |
DOIs | |
Publication status | Published - 6 Aug 2018 |
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CCDC 1496381: Experimental Crystal Structure Determination
Jiang, F. (Contributor), Siegler, M. A. (Contributor), Sun, X. (Contributor), Jiang, L. (Contributor), Guerra, C. F. (Contributor) & Bouwman, E. (Contributor), Unknown Publisher, 6 Aug 2018
DOI: 10.5517/ccdc.csd.cc1m73cb, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1m73cb&sid=DataCite
Dataset
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CCDC 1850287: Experimental Crystal Structure Determination
Jiang, F. (Contributor), Siegler, M. A. (Contributor), Sun, X. (Contributor), Jiang, L. (Contributor), Guerra, C. F. (Contributor) & Bouwman, E. (Contributor), Unknown Publisher, 6 Aug 2018
DOI: 10.5517/ccdc.csd.cc203cp6, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc203cp6&sid=DataCite
Dataset
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CCDC 1827153: Experimental Crystal Structure Determination
Jiang, F. (Contributor), Siegler, M. A. (Contributor), Sun, X. (Contributor), Jiang, L. (Contributor), Guerra, C. F. (Contributor) & Bouwman, E. (Contributor), Unknown Publisher, 6 Aug 2018
DOI: 10.5517/ccdc.csd.cc1zb9f1, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1zb9f1&sid=DataCite
Dataset