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.

Binary sulfur fluorides exhibit an interesting reactivity towards transition metal complexes. They open up routes for the generation of sulfur‐containing building blocks. Often ligands with particular properties can be constructed. This includes their ability to transfer sulfur atoms or polysulfide units as well as fluorination reactions. This Minireview provides an insight into the reactivity of the binary and ternary sulfur halides S2Cl2, SCl2, SF4, SF6 and SF5Cl towards transition‐metal compounds.

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

The facile access to the Vaska type fluorido complexes trans‐[Ir(F)(CO)(PR3)2] [6: R = Et, 7: R = Ph, 8: R = iPr, 9: R = Cy, 10: R = tBu] was achieved by halide exchange at trans‐[Ir(Cl)(CO)(PR3)2] (1–5) with Me4NF. Furthermore, the reaction of complex 6 with SF4 gave cis,trans‐[Ir(F)2(SF3)(CO)(PEt3)2] (11), whereas 8–10 did not react. Reactivity studies revealed that 11 can selectively be manipulated at the sulfur atom by hydrolysis or fluoride abstraction to give cis,trans‐[Ir(F)2(SOF)(CO)(PEt3)2] (12) and cis,trans‐[Ir(F)2(SF2)(CO)(PEt3)2][AsF6] (13), respectively.

The reactivity of Ni(cod)2 in the presence of trialkylphosphines towards perfluorophenazine was investigated. Studies on the mechanism of the C–F activation process are reported.