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Polymeric cobalt(II) thiolato complexes-syntheses, structures and properties of ¹∞[Co(SMes)₂] and ¹∞[Co(SPh)₂NH₃]

Eichhöfer, Andreas; Buth, Gernot

Abstract (englisch): 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.

Zugehörige Institution(en) am KIT Institut für Nanotechnologie (INT)
Karlsruhe Nano Micro Facility (KNMF)
Institut für Photonenforschung und Synchrotronstrahlung (IPS)
Publikationstyp Zeitschriftenaufsatz
Jahr 2016
Sprache Englisch
Identifikator DOI: 10.1039/c6dt03098j
ISSN: 0300-9246, 1364-5447, 1470-479X, 1472-7773, 1477-9226, 1477-9234, 1568-0258, 1570-5854
URN: urn:nbn:de:swb:90-628787
KITopen ID: 1000062878
HGF-Programm 43.21.04; LK 01
Erschienen in Dalton transactions
Band 45
Heft 43
Seiten 17382-17391
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