Fluorination Reactions at a Platinum Carbene Complex: Reaction Routes to SF , S(=O)F and Fluorido Complexes

Overview

Journal Chemistry

Specialty Chemistry

Date 2021 Oct 11

PMID 34634177

Citations 4

Authors

Dilcan Dirican

Maria Talavera

Thomas Braun

Affiliations

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Abstract

The electron-rich Pt complex [Pt(IMes) ] (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 undergoes a rapid oxidative addition at Pt to yield trans-[Pt(F)(SF )(IMes) ]. A photolytic reaction of SF at [Pt(IMes) ] in the presence of IMes gave the fluorido complexes trans-[Pt(F) (IMes) ] and trans-[Pt(F)(SF )(IMes) ] along with trans-[Pt(F)(SOF)(IMes) ] 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) ] and trans-[Pt(F) (IMes) ] were synthesized independently by treatment of [Pt(IMes) ] with SOF or XeF . A reaction of [Pt(IMes) ] with a HF source gave trans-[Pt(H)(F)(IMes) ], and an intermediate bifluorido complex trans-[Pt(H)(FHF)(IMes) ] was identified. Compound trans-[Pt(H)(F)(IMes) ] converts in the presence of CsF into trans-[Pt(F)(IMes')(IMes)].

Citing Articles

Hydrogen Bonding in Platinum Indolylphosphine Polyfluorido and Fluorido Complexes.

Sander S, Cosgrove E, Muller R, Kaupp M, Braun T Chemistry. 2022; 29(7):e202202768.

PMID: 36327144 PMC: 10107128. DOI: 10.1002/chem.202202768.

Platinum-Catalyzed Hydrofluorination of Alkynes: Hydrogen Bonding to Indolylphosphine Ligands to Provide Fluoride Reactivity.

Sander S, Braun T Angew Chem Int Ed Engl. 2022; 61(30):e202204678.

PMID: 35420731 PMC: 9401575. DOI: 10.1002/anie.202204678.

Reactivity of Xantphos-Type Rhodium Complexes Towards SF : SF Versus SF Complex Generation.

Wozniak M, Sander S, Cula B, Ahrens M, Braun T Chemistry. 2022; 28(33):e202200626.

PMID: 35420718 PMC: 9322540. DOI: 10.1002/chem.202200626.

Fluorination Reactions at a Platinum Carbene Complex: Reaction Routes to SF , S(=O)F and Fluorido Complexes.

Dirican D, Talavera M, Braun T Chemistry. 2021; 27(70):17707-17712.

PMID: 34634177 PMC: 9298267. DOI: 10.1002/chem.202103311.

References

Weitkamp R, Neumann B, Stammler H, Hoge B . Non-Coordinated Phenolate Anions and Their Application in SF Activation. Chemistry. 2020; 27(21):6460-6464. PMC: 8247349. DOI: 10.1002/chem.202003504. View

Eisenstein O, Milani J, Perutz R . Selectivity of C-H Activation and Competition between C-H and C-F Bond Activation at Fluorocarbons. Chem Rev. 2017; 117(13):8710-8753. DOI: 10.1021/acs.chemrev.7b00163. View

McTeague T, Jamison T . Photoredox Activation of SF for Fluorination. Angew Chem Int Ed Engl. 2016; 55(48):15072-15075. DOI: 10.1002/anie.201608792. View

Buss F, Muck-Lichtenfeld C, Mehlmann P, Dielmann F . Nucleophilic Activation of Sulfur Hexafluoride: Metal-Free, Selective Degradation by Phosphines. Angew Chem Int Ed Engl. 2018; 57(18):4951-4955. DOI: 10.1002/anie.201713206. View

Zamostna L, Braun T, Braun B . S-F and S-C activation of SF6 and SF5 derivatives at rhodium: conversion of SF6 into H2S. Angew Chem Int Ed Engl. 2014; 53(10):2745-9. DOI: 10.1002/anie.201308254. View

Dubinsky-Davidchik I, Goldberg I, Vigalok A, Vedernikov A . Selective aryl-fluoride reductive elimination from a platinum(IV) complex. Angew Chem Int Ed Engl. 2015; 54(42):12447-51. DOI: 10.1002/anie.201503116. View

Schaub T, Fischer P, Steffen A, Braun T, Radius U, Mix A . C-F activation of fluorinated arenes using NHC-stabilized nickel(0) complexes: selectivity and mechanistic investigations. J Am Chem Soc. 2008; 130(29):9304-17. DOI: 10.1021/ja074640e. View

Yahav A, Goldberg I, Vigalok A . Synthesis of the elusive (R3P)2MF2 (M = Pd, Pt) complexes. J Am Chem Soc. 2003; 125(45):13634-5. DOI: 10.1021/ja0377753. View

Dirican D, Talavera M, Braun T . Fluorination Reactions at a Platinum Carbene Complex: Reaction Routes to SF , S(=O)F and Fluorido Complexes. Chemistry. 2021; 27(70):17707-17712. PMC: 9298267. DOI: 10.1002/chem.202103311. View

10.

Berger J, Braun T, Ahrens T, Klaring P, Laubenstein R, Braun-Cula B . The Versatile Behavior of Platinum Alkyne Complexes towards XeF : Formation of Fluorovinyl and Fluorido Complexes. Chemistry. 2017; 23(37):8886-8900. DOI: 10.1002/chem.201700403. View

11.

Akhgarnusch A, Hockendorf R, Beyer M . Thermochemistry of the Reaction of SF6 with Gas-Phase Hydrated Electrons: A Benchmark for Nanocalorimetry. J Phys Chem A. 2015; 119(39):9978-85. DOI: 10.1021/acs.jpca.5b06975. View

12.

Dubinsky-Davidchik I, Goldberg I, Vigalok A, Vedernikov A . Unprecedented 1,3-migration of the aryl ligand in metallacyclic aryl α-naphthyl Pt(IV) difluorides to produce β-arylnaphthyl Pt(II) complexes. Chem Commun (Camb). 2013; 49(33):3446-8. DOI: 10.1039/c3cc41079j. View

13.

Fortman G, Scott N, Linden A, Stevens E, Dorta R, Nolan S . Unusual reactivities of N-heterocyclic carbenes upon coordination to the platinum(II)-dimethyl moiety. Chem Commun (Camb). 2010; 46(7):1050-2. DOI: 10.1039/b920482b. View

14.

Kuehnel M, Lentz D, Braun T . Synthesis of fluorinated building blocks by transition-metal-mediated hydrodefluorination reactions. Angew Chem Int Ed Engl. 2013; 52(12):3328-48. DOI: 10.1002/anie.201205260. View

15.

Grushin V . The organometallic fluorine chemistry of palladium and rhodium: studies toward aromatic fluorination. Acc Chem Res. 2009; 43(1):160-71. DOI: 10.1021/ar9001763. View

16.

Smith D, Beweries T, Blasius C, Jasim N, Nazir R, Nazir S . The Contrasting Character of Early and Late Transition Metal Fluorides as Hydrogen Bond Acceptors. J Am Chem Soc. 2015; 137(36):11820-31. DOI: 10.1021/jacs.5b07509. View

17.

Brosi F, Vent-Schmidt T, Kieninger S, Schloder T, Beckers H, Riedel S . Polyfluorides and Neat Fluorine as Host Material in Matrix-Isolation Experiments. Chemistry. 2015; 21(46):16455-62. DOI: 10.1002/chem.201502849. View

18.

Zhao S, Wang R, Nguyen H, Becker J, Gagne M . Electrophilic fluorination of cationic Pt-aryl complexes. Chem Commun (Camb). 2011; 48(3):443-5. PMC: 3449214. DOI: 10.1039/c1cc15006e. View

19.

Braun T, Noveski D, Ahijado M, Wehmeier F . Hydrodefluorination of pentafluoropyridine at rhodium using dihydrogen: detection of unusual rhodium hydrido complexes. Dalton Trans. 2007; (34):3820-5. DOI: 10.1039/b706846h. View

20.

Miro J, Del Pozo C . Fluorine and Gold: A Fruitful Partnership. Chem Rev. 2016; 116(19):11924-11966. DOI: 10.1021/acs.chemrev.6b00203. View