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Open AccessArticle

Diferrocenyl Thioketone: Reactions with (Bisphosphane)Pt(0) Complexes—Electrochemical and Computational Studies

1
Institute for Inorganic and Analytical Chemistry, Friedrich Schiller University Jena, Humboldstrasse 8, 07743 Jena, Germany
2
Clinic of Nuclear Medicine, University Hospital Jena, Am Klinikum 1, 07747 Jena, Germany
3
Department of Physical Chemistry, Faculty of Chemistry, University of Łódź, Pomorska 163/165, 90236 Lodz, Poland
4
Department of Inorganic and Analytical Chemistry, Faculty of Chemistry, University of Łódź, Tamka 12, 91403 Łódź, Poland
5
Department of Organic and Applied Chemistry, Faculty of Chemistry, University of Łódź, Tamka 12, 91403 Łódź, Poland
*
Authors to whom correspondence should be addressed.
Materials 2019, 12(17), 2832; https://doi.org/10.3390/ma12172832
Received: 31 July 2019 / Revised: 26 August 2019 / Accepted: 29 August 2019 / Published: 3 September 2019
(This article belongs to the Special Issue Current Problems of the Organic Chemistry of Sulfur and Selenium)
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. View Full-Text
Keywords: thioketones; ferrocene; Pt(0) complexes; platinathiiranes; cyclic voltammetry; DFT calculations thioketones; ferrocene; Pt(0) complexes; platinathiiranes; cyclic voltammetry; DFT calculations
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MDPI and ACS Style

Gröber, S.; Matczak, P.; Domagała, S.; Weisheit, T.; Görls, H.; Düver, A.; Mlostoń, G.; Weigand, W. Diferrocenyl Thioketone: Reactions with (Bisphosphane)Pt(0) Complexes—Electrochemical and Computational Studies. Materials 2019, 12, 2832.

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