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 provide 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.