The activation of SF at [Pt(PR ) ] R=Cy, iPr complexes in the presence of PR led selectively and in an unprecedented reaction route to the generation of the SF complexes trans-[Pt(F)(SF )(PR ) ]. These can also be synthesized from SF and the SF derivative trans-[Pt(F)(SF )(PCy ) ][BF ] was characterized by X-ray crystallography. trans-[Pt(F)(SF )(PR ) ] complexes are useful tools for deoxyfluorination reactions and novel fluorido complexes bearing a SOF ligand are formed. Based on these studies a process for the deoxyfluorination of ketones was developed with SF as fluorinating agent.

As a rather inert gas, sulfur hexafluoride is still used as a dielectric in high-voltage power applications despite its high global warming potential. Its activation at transition metal complexes has been reported, but the fate of the sulfur-containing products is often unknown. The activation of SF 6 at [Rh(H){ tBu xanPOP}] ( tBu xanPOP = 9,9-dimethyl-4,5-bis(ditertbutylphosphino)xanthene) at room temperature leads to the generation of the bifluorido complex [Rh(FHF){ tBu xanPOP}]. A subsequent regeneration of [Rh(H){ tBu xanPOP}] completes a cyclic process for the degradation of SF 6 . Furthermore, the SF 6 activation at [Rh(H){ tBu xanPOP}] in the presence of triethylsilane as a hydrogen source is described, which leads to the formation of the fluorido complex [Rh(F) 2 (H){ tBu xanPOP}] as well as [Rh(SH)-{ tBu xanPOP}] and S(SiEt 3 ) 2 as sulfur-containing products.

Gold­(I) fluorido complexes with phosphine ligands have been synthesized from their respective iodido precursors. The bonding situation in comparison between complexes bearing phosphines and N-heterocyclic carbenes (NHCs) was explored quantum-chemically, obtaining similar results for both. Calculations of the 19F NMR chemical shifts match the experimental values well, including the approximately 40 ppm low-field shifts for the phosphine complexes compared to the NHC complexes, in spite of similar negative charges on fluorine. The reactivity of the highly water-sensitive gold­(I) fluorido complexes was studied, resulting in substitution at the metal using trimethylsilyl reagents. The compounds studied were characterized using NMR as well as X-ray diffraction methods.

A general route to access the Vaska type fluorido complexes (6), Ph (7), iPr (8), Cy (9), tBu (10)] was developed by treatment of trans-[Rh(Cl)(CO)(PR 3 ) 2 ] (1-5) with Me 4 NF. The molecular structures of 8 and 9 were determined by

A series of isotopologues of the siloxanediol Mes Si(OH)(μ-O)Si(OH)Mes (3 a) (Mes=2,4,6-trimethylphenyl) were synthesized by reactions of the corresponding disiloxane precursors Mes Si(μ-O) SiMes (2 a), Mes Si(μ- O) SiMes (2 b) or Mes Si(μ- O) SiMes (2 c) with an excess of H O, H O or H O. NMR and IR signal assignments for the siloxanediols in benzene are supported by quantum-chemical calculations, which indicate small energy differences between trans and cis conformers, the latter of which exhibits an intramolecular hydrogen bond. H NMR as well as IR data suggest the presence of a mixture of both conformers in C D . Hydrogen-bonded adducts of Mes Si(OH)(μ-O)Si(OH)Mes with ethers such as diethylether, dimethoxyethane or dioxane were observed in the solid state, where they form polymeric chain-like structures. The latter appear to be stable only in the crystal. O{ H} NMR and IR data in THF solution suggest an interaction of 3 a with at least one THF molecule, whereas diethylether appears not to interact. Water adducts form neither in solution nor in the solid state as indicated by NMR and ATR IR data. O{ H} NMR and ESI-MS experiments illustrate the remarkably high stability of the siloxanediols towards water and show no evidence for intra- or intermolecular oxygen-exchange reactions. In marked contrast, a stepwise exchange of all three oxygen atoms-including the one in the Si-O-Si bridge-occurred in the gas phase, when [Mes Si( OH)(μ- O)Si( O)Mes ] was treated with H O in the hexapole of an ESI FT-ICR mass spectrometer. The scrambling between the bridging and the other oxygen atoms likely proceeds through cyclic Si O intermediates.