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Fluorination Reactions at a Platinum Carbene Complex: Reaction Routes to SF 3 , S(=O)F and Fluorido Complexes
Author(s) -
Dirican Dilcan,
Talavera Maria,
Braun Thomas
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202103311
Subject(s) - imes , chemistry , carbene , ligand (biochemistry) , organic chemistry , catalysis , biochemistry , receptor
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 SF 4 undergoes a rapid oxidative addition at Pt 0 to yield trans ‐[Pt(F)(SF 3 )(IMes) 2 ]. A photolytic reaction of SF 6 at [Pt(IMes) 2 ] in the presence of IMes gave the fluorido complexes trans ‐[Pt(F) 2 (IMes) 2 ] and trans ‐[Pt(F)(SF 3 )(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 SOF 2 or XeF 2 . 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)].