Fluorination Reactions at a Platinum Carbene Complex: Reaction Routes to SF3, S(=O)F and Fluorido Complexes. Issue 70 (29th October 2021)

• Record Type: Journal Article
• Authors: Dirican, Dilcan; Talavera, Maria; Braun, Thomas
• Is Part Of: Chemistry. Volume 27:Issue 70(2021)
• Page Start: 17707
• Page End: 17712
• Publication Date: 2021-10-29
• Subjects: fluorido complexes -- fluorine -- platinum -- S−F activation -- sulfur fluorides; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202103311
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: The electron‐rich Pt complex [Pt(IMes)2 ] (IMes: [1, 3‐bis(2, 4, 6‐trimethylphenyl)‐2‐imidazolinylidine]) can be used as precursor for the syntheses of a variety of fluorido ligand containing compounds. The sulfur fluoride SF4 undergoes a rapid oxidative addition at Pt 0 to yield trans ‐[Pt(F)(SF3 )(IMes)2 ]. A photolytic reaction of SF6 at [Pt(IMes)2 ] in the presence of IMes gave the fluorido complexes trans ‐[Pt(F)2 (IMes)2 ] and trans ‐[Pt(F)(SF3 )(IMes)2 ] along with trans ‐[Pt(F)(SOF)(IMes)2 ] and trans ‐[Pt(F)(IMes')(IMes)] (IMes': cyclometalated IMes ligand), the latter being products produced by reaction with adventitious water. trans ‐[Pt(F)(SOF)(IMes)2 ] and trans ‐[Pt(F)2 (IMes)2 ] were synthesized independently by treatment of [Pt(IMes)2 ] with SOF2 or XeF2 . A reaction of [Pt(IMes)2 ] with a HF source gave trans ‐[Pt(H)(F)(IMes)2 ], and an intermediate bifluorido complex trans ‐[Pt(H)(FHF)(IMes)2 ] was identified. Compound trans ‐[Pt(H)(F)(IMes)2 ] converts in the presence of CsF into trans ‐[Pt(F)(IMes')(IMes)]. Abstract : Studies on the reactivity of thionyl fluoride and sulfur tetrafluoride towards the Pt(0) complex [Pt(IMes)2 ] led to the generation of Pt(II) SF3 and SOF complexes. The activation of SF6 at [Pt(IMes)2 ] gave a variety of fluorido complexes, some of which were synthesized independently by fluorination with HF or XeF2 .