Eichhöfer Andreas, Buth Gernot
Institut für Nanotechnologie, Karlsruher Institut für Technologie (KIT), Campus Nord, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.
Institut für Photonenforschung und Synchrotronstrahlung, Karlsruher Institut für Technologie (KIT), Campus Nord, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.
Dalton Trans. 2016 Nov 1;45(43):17382-17391. doi: 10.1039/c6dt03098j.
Reactions of [Co(N(SiMe))thf] with 2.1 equiv. of MesSH (Mes = CH-2,4,6-(CH)) yield dark brown crystals of the one dimensional chain compound [Co(SMes)]. In contrast reactions of [Co(N(SiMe))thf] with 2.1 equiv. of PhSH result in the formation of a dark brown almost X-ray amorphous powder of 'Co(SPh)'. Addition of aliquots of CHOH to the latter reaction resulted in the almost quantitative formation of crystalline ammonia thiolato complexes either [Co(SPh)(NH)] or [Co(SPh)NH]. Single crystal XRD reveals that [Co(SPh)NH] forms one-dimensional chains in the crystal via μ-SPh bridges whereas [Co(SPh)(NH)] consists at a first glance of isolated distorted tetrahedral units. Magnetic measurements suggest strong antiferromagnetic coupling for the two chain compounds [Co(SMes)] (J = -38.6 cm) and [Co(SPh)NH] (J = -27.1 cm). Interestingly, also the temperature dependence of the susceptibility of tetrahedral [Co(SPh)(NH)] 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)(NH)] and [Co(SPh)NH] reveals two well separated cleavage processes for NH and SPh upon heating accompanied by the stepwise formation of 'Co(SPh)' and cobalt sulfide.
