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.

The complex trans-[Pt(F)(SF )(PCy ) ] (1) shows a diverse reactivity pattern at the SF ligand towards ethanol and Me SiOEt. This led by deoxyfluorination or alcoholysis to the generation of platinum complexes bearing a metal-bound S(O)F or S(OEt) group. For the latter reaction trans-[Pt(F){S(F)(OEt) }(PCy ) ] is suggested as an intermediate. In reactivity studies of trans-[Pt(F)(SF )(PCy ) ][BF ] the complex [Pt(F){S(F)(OEt)}(PCy ) ][BF ] was prepared, which does not react with ethanol.

Stoichiometric reactions of SF5 functionalized bromo or iodo aromatics at [Pd(PiPr3)2] (1) led to the oxidative addition products 3, 5 and 7. They were converted into their corresponding palladium fluorido complexes, which reacted readily with bis(pinacolato)diboron (B2pin2) to give the borylated SF5 aromatic compounds. Based on these studies a catalytic borylation of SF5 organyls was developed.

The activation of SF6 at [Pt(PR3)2] R=Cy, iPr complexes in the presence of PR3 led selectively and in an unprecedented reaction route to the generation of the SF3 complexes trans‐[Pt(F)(SF3)(PR3)2]. These can also be synthesized from SF4 and the SF2 derivative trans‐[Pt(F)(SF2)(PCy3)2][BF4] was characterized by X‐ray crystallography. trans‐[Pt(F)(SF3)(PR3)2] 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 SF6 as fluorinating agent.