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Polymeric cobalt(II) thiolato complexes-syntheses, structures and properties of $^1_{\infty}$[Co(SMes)$_2$] and $^1_{\infty}$[Co(SPh)$_2$NH$_3$]

Eichhöfer, Andreas 1; Buth, Gernot 2
1 Institut für Nanotechnologie (INT), Karlsruher Institut für Technologie (KIT)
2 Institut für Photonenforschung und Synchrotronstrahlung (IPS), Karlsruher Institut für Technologie (KIT)

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.

Volltext §
DOI: 10.5445/IR/1000062878
DOI: 10.1039/c6dt03098j
Zitationen: 9
Zitationen: 9
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Nanotechnologie (INT)
Institut für Photonenforschung und Synchrotronstrahlung (IPS)
Karlsruhe Nano Micro Facility (KNMF)
Publikationstyp Zeitschriftenaufsatz
Publikationsjahr 2016
Sprache Englisch
Identifikator ISSN: 0300-9246, 1364-5447, 1470-479X, 1472-7773, 1477-9226, 1477-9234, 1568-0258, 1570-5854
KITopen-ID: 1000062878
HGF-Programm 43.21.04 (POF III, LK 01) Molecular Engineering
Erschienen in Dalton transactions
Verlag Royal Society of Chemistry (RSC)
Band 45
Heft 43
Seiten 17382-17391
Bemerkung zur Veröffentlichung RSC geförderter Open Access-Artikel
Nachgewiesen in Scopus
Web of Science
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