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Diferrocenyl Thioketone: Reactions with (Bisphosphane)Pt(0) Complexes-Electrochemical and Computational Studies. | LitMetric

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Article 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, bearing three Fc-units, was prepared starting with [bis(diphenylphosphino)ferrocene] Pt(0(-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 CHCl solutions. For comparison, the cyclic voltammogram for diferrocenyl thioketoneas a mixed-valent (Fe-Fe) 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.

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http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6747965PMC
http://dx.doi.org/10.3390/ma12172832DOI Listing

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