Formation and C–F bond functionalization of [P,N]-ligated perfluoronickelacyclopentanes

Giffin, Kaitie A.; Pua, Lorraine A.; Korobkov, Ilia; Baker, R. Tom

doi:10.1016/j.poly.2018.10.024

Cited by 6 publications

(2 citation statements)

References 29 publications

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“…The ability of ligands to migrate from the nickel to the α-carbon was examined further in our group by Giffin, who treated a PS-ligated metallacycle with TMSOTf to find that the phosphine migrates as expected to furnish Cα-phosphonium salt (Scheme B; TMSOTf = Me 3 SiOSO 2 CF 3 ). Similar reactivity was subsequently demonstrated using a PN ligand . Next, an NHC-ligated three-coordinate metallacycle prepared by Andrella was shown to undergo Cα–F abstraction by TMSOTf, accompanied by ring contraction to a perfluoroocyclobutyl complex (Scheme C) …”

Section: Introductionmentioning

confidence: 64%

“…Similar reactivity was subsequently demonstrated using a PN ligand. 17 Next, an NHC-ligated three-coordinate metallacycle prepared by Andrella was shown to undergo Cα−F abstraction by TMSOTf, accompanied by ring contraction to a perfluoroocyclobutyl complex (Scheme 1C). 18 The ability of tetrafluoroethylene to form ring-expanded metallacycles with nickel has been leveraged extensively for catalysis by Ogoshi et al, with multicomponent couplings between TFE and aldehydes, 19,20 styrenes, 21 alkynes, 22 and ethylene 23 proceeding through seven-membered metallacycles.…”

Section: ■ Introductionmentioning

confidence: 99%

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Nickel-Catalyzed Homologation of Vinylidene Difluoride (CH₂═CF₂): Selective β-F vs β-H Elimination

et al. 2022

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Hydrofluoroolefins (HFOs) constitute the newest generation of fluorocarbon refrigerants and foam-blowing agents due to their reduced global warming potential vs their saturated analogues. To identify new synthetic routes to HFOs, we show that reactions of bulky Ni(0) phosphine and −NHC complexes with vinylidene difluoride (VF2) afford μ-fluoro-1,1,3-trifluorobut-3enyl Ni complexes. Moreover, addition of triisopropylsilane allows for reductive elimination of the reduced product�2,4,4-trifluoro-1-butene�demonstrating the Ni-catalyzed hydrodefluorodimerization of VF2. Accompanying DFT calculations identify the Tshaped nickelacyclopentane intermediate that spontaneously undergoes selective intramolecular β-F (vs β-H) elimination.

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Section: Introductionmentioning

confidence: 64%

Section: ■ Introductionmentioning

confidence: 99%

Nickel-Catalyzed Homologation of Vinylidene Difluoride (CH₂═CF₂): Selective β-F vs β-H Elimination

et al. 2022

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Pincer‐Supported Perfluororhodacyclopentanes: High Nucleophilicity of the M−C^F Bond

et al. 2022

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Perfluororhodacyclopentane supported by PBP pincer ligand PBP‐RhIII(CF2)4 (2) was prepared from PBP‐RhI‐PPh3 (1) and tetrafluoroethylene (TFE). By scXRD analysis, it was revealed that the Rh−CF bond trans to the boryl ligand was largely elongated compared to the one in the apical position. Although M−CF bonds of perfluorometallacyclopentanes are known to be very stable, 2 shows high reactivity toward hydrogenolysis, iodinolysis and protonolysis, thanks to the strong trans‐effect of the highly σ‐donating boryl ligand. Analogous PCP pincer complex PCP−RhIII(CF2)4 (4) showed slower reaction rate both in oxidative cyclization with TFE and hydrogenolysis of Rh−CF bond. Catalytic production of 1,1,2,2,3,3,4,4‐octafluorobutane from two TFE and hydrogen in one pot was achieved via repetitive oxidative cyclization of TFE and Rh followed by the hydrogenolysis of Rh−CF bonds. This report demonstrates the possible application of PBP‐pincer skeleton to the preparation of fluorinated compounds from TFE.

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What's Next for First Row Fluorometallacycles?

Baker,

Mangin

2024

Angewandte Chemie

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Hydrocarbon‐derived metallacycles have been identified as key intermediates in a host of catalyzed transformations of unsaturated organic substrates. In contrast, our knowledge of analogous reactivity of fluorometallacycles is underdeveloped and largely confined to first row metals. Our summary of recent advances aims to inform young investigators of the exciting challenges offered by this pursuit.

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Formation and C–F bond functionalization of [P,N]-ligated perfluoronickelacyclopentanes

Cited by 6 publications

References 29 publications

Nickel-Catalyzed Homologation of Vinylidene Difluoride (CH₂═CF₂): Selective β-F vs β-H Elimination

Nickel-Catalyzed Homologation of Vinylidene Difluoride (CH₂═CF₂): Selective β-F vs β-H Elimination

Pincer‐Supported Perfluororhodacyclopentanes: High Nucleophilicity of the M−C^F Bond

What's Next for First Row Fluorometallacycles?

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Formation and C–F bond functionalization of [P,N]-ligated perfluoronickelacyclopentanes

Cited by 6 publications

References 29 publications

Nickel-Catalyzed Homologation of Vinylidene Difluoride (CH2═CF2): Selective β-F vs β-H Elimination

Nickel-Catalyzed Homologation of Vinylidene Difluoride (CH2═CF2): Selective β-F vs β-H Elimination

Pincer‐Supported Perfluororhodacyclopentanes: High Nucleophilicity of the M−CF Bond

What's Next for First Row Fluorometallacycles?

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Product

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Nickel-Catalyzed Homologation of Vinylidene Difluoride (CH₂═CF₂): Selective β-F vs β-H Elimination

Nickel-Catalyzed Homologation of Vinylidene Difluoride (CH₂═CF₂): Selective β-F vs β-H Elimination

Pincer‐Supported Perfluororhodacyclopentanes: High Nucleophilicity of the M−C^F Bond