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.

Three different complexes of the (dppbe)Pt(η 2 -tolane) [dppbe = 1,2-bis(diphenylphosphino)benzene] type bearing CF 3 groups at the 2,2Ј-(4a), 3,3Ј-(4b), and 4,4Ј-positions (4c) of the tolane ligand were synthesized. A one-pot procedure for the synthesis of the tolane ligands from 2-methyl-3-butyn-2-ol as the acetylene derivative was developed. To investigate their selective photochemical carbon-carbon bond cleavage, 4a-4c were exposed to UV light (1 W, 356 nm) in the solid state and in solution. The oxidative addition of the [a]149 C(sp)-C(sp 2 ) bond to the (dppbe)Pt 0 complex fragment to form the corresponding CF 3 -substituted (dppbe)Pt(ethynylphenyl)(phenyl) complex was followed by 31 P{ 1 H} NMR spectroscopy. The reactivity of 4a-4c relative to the position of the CF 3 substituent and the torsion angle between the substituted phenyl rings is discussed. All of the complexes were isolated and characterized by various spectroscopic methods and additionally by single-crystal X-ray diffractometry. Scheme 1. Synthesis of tolane ligands 3a-3c by a one-pot procedure. (i) [Pd(PPh 3 ) 2 Cl 2 ], CuI, diisopropylamine (DIPA); (ii) KOH, MeOH; (iii) 1 equiv. of 1a-1c. 155 found C 58.26, H 3.45. MS (DEI): m/z = 955 [M + H] + , 936 [M -F] + , 640 [(dppbe)Pt] + .