Routes to Pt Derivatives of High‐Valent Sulfur Oxofluorides S(═O)₂F, S(═O)F₂, and S(═O)F₃ by Fluorination and Oxygenation

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