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Issue 43, 2016
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Polymeric cobalt(II) thiolato complexes – syntheses, structures and properties of 1[Co(SMes)2] and 1[Co(SPh)2NH3]

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Abstract

Reactions of [Co(N(SiMe3)2)2thf] with 2.1 equiv. of MesSH (Mes = C6H2-2,4,6-(CH3)3) yield dark brown crystals of the one dimensional chain compound 1[Co(SMes)2]. In contrast reactions of [Co(N(SiMe3)2)2thf] with 2.1 equiv. of PhSH result in the formation of a dark brown almost X-ray amorphous powder of ‘Co(SPh)2’. Addition of aliquots of CH3OH to the latter reaction resulted in the almost quantitative formation of crystalline ammonia thiolato complexes either [Co(SPh)2(NH3)2] or 1[Co(SPh)2NH3]. Single crystal XRD reveals that 1[Co(SPh)2NH3] forms one-dimensional chains in the crystal via μ2-SPh bridges whereas [Co(SPh)2(NH3)2] consists at a first glance of isolated distorted tetrahedral units. Magnetic measurements suggest strong antiferromagnetic coupling for the two chain compounds 1[Co(SMes)2] (J = −38.6 cm−1) and 1[Co(SPh)2NH3] (J = −27.1 cm−1). Interestingly, also the temperature dependence of the susceptibility of tetrahedral [Co(SPh)2(NH3)2] shows an antiferromagnetic transition at around 6 K. UV-Vis-NIR spectra display d–d bands in the NIR region between 500 and 2250 nm. Thermal gravimetric analysis of [Co(SPh)2(NH3)2] and 1[Co(SPh)2NH3] reveals two well separated cleavage processes for NH3 and SPh2 upon heating accompanied by the stepwise formation of ‘Co(SPh)2’ and cobalt sulfide.

Graphical abstract: Polymeric cobalt(ii) thiolato complexes – syntheses, structures and properties of 1∞[Co(SMes)2] and 1∞[Co(SPh)2NH3]

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Publication details

The article was received on 04 Aug 2016, accepted on 27 Sep 2016 and first published on 27 Sep 2016


Article type: Paper
DOI: 10.1039/C6DT03098J
Citation: Dalton Trans., 2016,45, 17382-17391
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    Polymeric cobalt(II) thiolato complexes – syntheses, structures and properties of 1[Co(SMes)2] and 1[Co(SPh)2NH3]

    A. Eichhöfer and G. Buth, Dalton Trans., 2016, 45, 17382
    DOI: 10.1039/C6DT03098J

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