Nickel fluoro complexes as intermediates in catalytic cross-coupling reactions

Breyer, David; Berger, Josefine; Braun, Thomas; Mebs, Stefan

doi:10.1016/j.jfluchem.2012.06.025

Cited by 24 publications

(31 citation statements)

References 109 publications

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“…The resonance for the metal‐bound fluorido ligand appears in the 19 F{ 1 H} NMR spectrum (Figure ) as a doublet of doublets at high field with 195 Pt satellites ( δ =−206.9 ppm, 4 J (F,F)=3, 2 J (P,F trans )=179, 1 J (Pt,F)=156 Hz). The chemical shift as well as the coupling constant are characteristic of a transition‐metal‐bound fluorido ligand . The β‐fluorine atom causes a doublet with 195 Pt satellites at δ =−91.9 ppm ( 4 J (F,F)=3, 3 J (Pt,F)=260 Hz), which appears in the typical area for a β‐fluorovinyl ligand .…”

Section: Resultssupporting

confidence: 74%

The Versatile Behavior of Platinum Alkyne Complexes towards XeF₂: Formation of Fluorovinyl and Fluorido Complexes

Berger

Braun

Ahrens

et al. 2017

Chemistry A European J

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Reactions of platinum(0) tolane complexes, bearing a chelating ligand with P and N donor atoms, with the electrophilic fluorinating agent XeF give facile access to platinum(II) β-fluorovinyl fluorido complexes. A series of new platinum(II) β-fluorovinyl complexes have been synthesized and were structurally characterized. Further oxidation with XeF led to ortho-metalated platinum(IV) fluorido compounds. Additional reactions of platinum(0) tolane complexes, bearing a chelating P,P donor ligand, with XeF led to a variety of fluorido and fluorovinyl complexes.

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Section: Resultssupporting

confidence: 74%

The Versatile Behavior of Platinum Alkyne Complexes towards XeF₂: Formation of Fluorovinyl and Fluorido Complexes

Berger

Braun

Ahrens

et al. 2017

Chemistry A European J

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“…A comparable small P,P coupling constant for metal-bound phosphorus atoms in the cisposition was found for other platinum(II) complexes. 24,45,[77][78][79][80][81][82][83][84][85][86] The reactivity of [Pt(xantphos)(η 2 -PhCuCPh)] (2), which bears the xantphos ligand that exhibits a larger bite angle, was also investigated. Both P,F coupling constants are also observed in the 19 F{ 1 H} NMR spectrum as a doublet of doublets with 195 Pt satellites at δ −240 ppm ( 1 J Pt,F = 197 Hz).…”

Section: Resultsmentioning

confidence: 99%

Reactivity of platinum alkyne complexes towards N-fluorobenzenesulfonimide: formation of platinum compounds bearing a β-fluorovinyl ligand

et al. 2015

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The platinum(0) alkyne complexes [Pt(L)(η(2)-PhC[triple bond, length as m-dash]CPh)] 1-4 were synthesized by reactions of [Pt(cod)2] with diphenylacetylene and a phosphine ligand precursor (1: L = dcpe, 2: L = xantphos, 3: L = κ(2)-(P,N)-iPr2PC3H6NMe2, 4: L = κ(2)-(P,N)-iPr2PC2H4NMe2). Treatment of 1 or 4 with NFSI gave the complexes [Pt(F){N(SO2Ph)2}(dcpe)] (5) and [Pt(PhC[double bond, length as m-dash]CFPh){N(SO2Ph)2}{κ(2)-(P,N)-iPr2PC2H4NMe2}] (8), whereas the reactivity of 2 and 3 towards NFSI led to product mixtures. The compounds [Pt(F){N(SO2Ph)2}(xantphos)] (6a) as well as [Pt(PhC[double bond, length as m-dash]CFPh){N(SO2Ph)2}{κ(2)-(P,N)-iPr2PC2H4NMe2}] (7a) and [Pt(PhC[double bond, length as m-dash]CFPh)(F){κ(2)-(P,N)-iPr2PC2H4NMe2}] (7b) were clearly identified. Ligand exchange reactions at 8 resulted in the formation of the β-fluorovinyl platinum(ii) complexes [Pt(PhC[double bond, length as m-dash]CFPh){OC(O)CF3}{κ(2)-(P,N)-iPr2PC2H4NMe2}] (9), [Pt(PhC[double bond, length as m-dash]CFPh)(FHF){κ(2)-(P,N)-iPr2PC2H4NMe2}] (10) and [Pt(PhC[double bond, length as m-dash]CFPh)(F){κ(2)-(P,N)-iPr2PC2H4NMe2}] (11). Treatment of 8 with dihydrogen yielded the fluorinated olefin (Z)-(1-fluoroethene-1,2-diyl)dibenzene and [Pt{N(SO2Ph)2}(H){κ(2)-(P,N)-iPr2PC2H4NMe2}] (12).

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“…The difference in regiospecificity is postulated to be a result of steric factors. In a subsequent report, the Braun group also described the formation of a related P (52) [102]. Pentafluoropyridine underwent C-F activation in the 2-and 4-positions generating (55) and (56) (Eq.…”

Section: Stoichiometric Examplesmentioning

confidence: 97%

Activation and Formation of Aromatic C–F Bonds

LaBerge

Love

2015

Topics in Organometallic Chemistry

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The presence of aryl C-F bonds in pharmaceuticals and agrochemicals is increasing rapidly. Incorporation of a fluorine substituent into biologically relevant molecules yields many benefits such as decreased metabolism, solubility, hydrophobicity and decreased negative side effects. Since there are no known examples of naturally occurring aryl fluorides all must be accessed through chemical synthesis. The formation and activation of aryl C-F bonds is a challenging endeavor, nevertheless several strategies are possible. Recent developments towards the synthesis of fluoroaromatics, as well as routes to selectively remove fluorine from polyfluoroaromatics are surveyed.

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Nickel fluoro complexes as intermediates in catalytic cross-coupling reactions

Cited by 24 publications

References 109 publications

The Versatile Behavior of Platinum Alkyne Complexes towards XeF₂: Formation of Fluorovinyl and Fluorido Complexes

The Versatile Behavior of Platinum Alkyne Complexes towards XeF₂: Formation of Fluorovinyl and Fluorido Complexes

Reactivity of platinum alkyne complexes towards N-fluorobenzenesulfonimide: formation of platinum compounds bearing a β-fluorovinyl ligand

Activation and Formation of Aromatic C–F Bonds

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Nickel fluoro complexes as intermediates in catalytic cross-coupling reactions

Cited by 24 publications

References 109 publications

The Versatile Behavior of Platinum Alkyne Complexes towards XeF2: Formation of Fluorovinyl and Fluorido Complexes

The Versatile Behavior of Platinum Alkyne Complexes towards XeF2: Formation of Fluorovinyl and Fluorido Complexes

Reactivity of platinum alkyne complexes towards N-fluorobenzenesulfonimide: formation of platinum compounds bearing a β-fluorovinyl ligand

Activation and Formation of Aromatic C–F Bonds

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The Versatile Behavior of Platinum Alkyne Complexes towards XeF₂: Formation of Fluorovinyl and Fluorido Complexes

The Versatile Behavior of Platinum Alkyne Complexes towards XeF₂: Formation of Fluorovinyl and Fluorido Complexes