Redox Interconversion between Cobalt(III) Thiolate and Cobalt(II) Disulfide Compounds

Inorganic Chemistry
Feng JiangElisabeth Bouwman

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 [CoII2(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 [CoII2(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 co...Continue Reading

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Methods Mentioned

BETA
X-ray
NMR

Software Mentioned

AFIX
SHELXS
COSMO
CrysAlisPro
Amsterdam Density Functional ( ADF )
SHELXL
GPES4

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