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Keywords = platinathiiranes

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18 pages, 4320 KiB  
Article
Diferrocenyl Thioketone: Reactions with (Bisphosphane)Pt(0) Complexes—Electrochemical and Computational Studies
by Sebastian Gröber, Piotr Matczak, Sławomir Domagała, Thomas Weisheit, Helmar Görls, Annika Düver, Grzegorz Mlostoń and Wolfgang Weigand
Materials 2019, 12(17), 2832; https://doi.org/10.3390/ma12172832 - 3 Sep 2019
Cited by 5 | Viewed by 3762
Abstract
Diferrocenyl thioketone reacts smoothly with (bisphosphane)Pt(0) complexes in toluene solution at room temperature yielding 1:1 adducts identified as ferrocenyl (Fc) functionalized platinathiiranes. Their structures were unambiguously confirmed by means of spectroscopic methods as well as by X-ray diffraction analysis. A unique, ferrocene-rich platinathiirane, [...] Read more.
Diferrocenyl thioketone reacts smoothly with (bisphosphane)Pt(0) complexes in toluene solution at room temperature yielding 1:1 adducts identified as ferrocenyl (Fc) functionalized platinathiiranes. Their structures were unambiguously confirmed by means of spectroscopic methods as well as by X-ray diffraction analysis. A unique, ferrocene-rich platinathiirane, bearing three Fc-units, was prepared starting with [bis(diphenylphosphino)ferrocene] Pt(0(η2-norbornene). For comparison, a similar platinathiirane with one Fc-unit was obtained from the reaction of the latter complex with thiobenzophenone. Quantum-chemical calculations were carried out to describe the bonding pattern and frontier molecular orbitals of the ferrocene-rich platinathiirane complexes. These calculations confirmed that the C=S bond loses its formally double-bond character upon complexation (bisphosphane)Pt(0). Cyclic voltammetry measurements were performed to characterize the obtained platinathiiranes in CH2Cl2 solutions. For comparison, the cyclic voltammogram for diferrocenyl thioketoneas a mixed-valent (FeII-FeIII) compound was also recorded and analyzed. The results point out to a diffusion controlled electrode process in case of differocenyl thioketone and mixed diffusion and adsorption controlled electrode process in the case of the studied platinathiiranes. Full article
(This article belongs to the Special Issue Current Problems of the Organic Chemistry of Sulfur and Selenium)
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