Routes to Pt Derivatives of High‐Valent Sulfur Oxofluorides S(═O)2F, S(═O)F2, and S(═O)F3 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)2F, S(═O)F2, and S(═O)F3 by oxygenation or fluorination steps. The Pt(II) fluorido complex trans‐[Pt(F)(SOF)(PCy3)2] (2) reacts with the Davis reagent (3‐phenyl‐2‐(phenylsulfonyl)‐1,2‐oxaziridine) to yield the sulfuryl fluorido complex trans‐[Pt(F)(SO2F)(PCy3)2] (4). Notably, the electrophilic fluorinating agent NFSI (N‐fluorobenzenesulfonimide) reacts with 2 to form trans‐[Pt(F)(SOF2)(PCy3)2][NFSO2Ph] (5a). By nucleophilic fluorination with TMAF (Me4NF) it is possible to fluorinate the sulfur center once more to give the complex trans‐[Pt(F)(SOF3)(PCy3)2] (6) bearing an unprecedented SOF3 ligand. Above 283 K, complex 6 shows a decomposition of the SOF3 moiety to form trans‐[Pt(F)2(PCy3)2] (7) and SOF2. The described complexes could represent a previously unknown class of transfer reagents for high‐valent sulfur fluoride units.