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

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(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.

Ferrocenyl-substituted tetrahydrothiophenes via formal [3 + 2]-cycloaddition reactions of ferrocenyl thioketones with donor–acceptor cyclopropanes

“…The studied reactions displayed an interesting stereoselectivity and, in the case of 2,5-diaryl-substituted products 9, both aryl groups were exclusively located at the opposite sides of the ring plane. The described reactions supplement the recently reported synthetic applications of alkyl/ferrocenyl thioketones as attractive substrates for the synthesis of chiral ferrocene derivatives [22] and ferrocenyl-substituted platinathiiranes [23].…”

Metal–ligand bonding in tricarbonyliron(0) complexes bearing thiochalcone ligands

“…The thiochalcone ligands in these complexes are functionalized with hetaryl and ferrocenyl groups, which originates from our ongoing interest in aromatic and cycloaliphatic thioketones. [15][16][17][18][19][20][21][22] For comparison, the present study additionally includes model complex 7 (Chart 1) in order to assess the effect of aromatic groups Ar 1 and Ar 2 for 1-6. In the series of complexes 1-7, the metal-ligand bonds cover both the iron-thiadiene interaction and three iron-carbonyl bonds.…”

Structure of Diferrocenyl Thioketone: From Molecule to Crystal

“…In a broader perspective, this study may be important for further development of more complex structures containing the Fc 2 CS building block. In our very recent work we designed a test series of such structures; they were derived from Fc 2 CS and diverse (bisphosphane)Pt(0) complexes [107].…”