Routes to Pt Derivatives of High-Valent Sulfur Oxofluorides S(═O)F, S(═O)F, and S(═O)F by Fluorination and Oxygenation.

Metal derivatives of high-valent sulfur fluorides and oxofluorides can provid e fluorinated building blocks for materials science and bioactive compounds, but so far, such building blocks are elusive. The paper describes routes to access remarkable metal derivatives of S(═O)F, S(═O)F, and S(═O)F by oxygenation or fluorination steps. The Pt(II) fluorido complex trans-[Pt(F)(SOF)(PCy)] (2) reacts with the Davis reagent (3-phenyl-2-(phenylsulfonyl)-1,2-oxaziridine) to yield the sulfuryl fluorido complex trans-[Pt(F)(SOF)(PCy)] (4). Notably, the electrophilic fluorinating agent NFSI (N-fluorobenzenesulfonimide) reacts with 2 to form trans-[Pt(F)(SOF)(PCy)][NFSOPh] (5a). By nucleophilic fluorination with TMAF (MeNF) it is possible to fluorinate the sulfur center once more to give the complex trans-[Pt(F)(SOF)(PCy)] (6) bearing an unprecedented SOF ligand. Above 283 K, complex 6 shows a decomposition of the SOF moiety to form trans-[Pt(F)(PCy)] (7) and SOF. The described complexes could represent a previously unknown class of transfer reagents for high-valent sulfur fluoride units.