4.7 Article

Probing the redox-conversion of Co(II)-disulfide to Co(III)-thiolate complexes: the effect of ligand-field strength

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Summary: Here, we describe the synthesis of cobalt(II) disulfide compounds [Co-2(II)((LSSLx)-S-x)(mu-PO2F2)(2)](PF6)(2) and [Co-2(II)((LSSLx)-S-x)(NO3)(4)]. The crystal structures of these compounds reveal different coordination geometries for the cobalt(II) centers. [Co-2(II)((LSSLx)-S-x)(mu-PO2F2)(2)](PF6)(2) shows a distorted octahedral geometry, while [Co-2(II)((LSSL1)-S-x)(NO3)(4)] exhibits a distorted trigonal bipyramidal geometry. Furthermore, we found that [Co-2(II)((LSSLx)-S-x)(mu-PO2F2)(2)](PF6)(2) is stable in methanol and dichloromethane solution, but undergoes a redox conversion in acetonitrile forming a cobalt(III) thiolate compound.

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