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

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Journal
Angewandte Chemie International Edition
Published
2025-03-27
DOI
https://doi.org/10.1002/anie.202503153
Primary Topic
Fluorine in Organic Chemistry
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article
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Routes to Pt Derivatives of High‐Valent Sulfur Oxofluorides S(═O)2F, S(═O)F2, and S(═O)F3 by Fluorination and Oxygenation

Dilcan Dirican, Ouchan He, Ruben Jaeger, Mike Ahrens et al.
Angewandte Chemie International Edition
Fluorine in Organic Chemistry
article

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

Dilcan Dirican, Ouchan He, Ruben Jaeger, Mike Ahrens, Thomas Braun, Stefan Sander
article en

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

Angewandte Chemie International EditionVol. 64(23)
Humboldt-Universität zu Berlin (DE)
Openalex Percentile: Top 96%
Fluorine in Organic Chemistry
DOIOpen Access PDFOpenAlex
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Routes to Pt Derivatives of High‐Valent Sulfur Oxofluorides S(═O)<sub>2</sub>F, S(═O)F<sub>2</sub>, and S(═O)F<sub>3</sub> by Fluorination and Oxygenation — Dilcan Dirican, Ouchan He, et al. · Angewandte Chemie International Edition (2025) | TGRS Research Map | TGRS