Polycyclic fluoro-aromatic compounds. Part 10. Nucleophilic replacement of fluorine in heptafluoro-2-naphthyl-lithium

Burdon, J.; Gill, Harpal S.; Parsons, Ian W.

doi:10.1039/p19800002494

Cited by 12 publications

(3 citation statements)

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“…Predictably, these extensive applications of halogen derivatives of perfluoroarenes Ar F X (X = Br, I) prompted the development of a wealth of methods to access X-perfluoroarenes. As a rule, syntheses of Ar F X involve as reactants functionally substituted perfluoroarenes, Ar F R (R = CO 2 H, , NH 2 , NHNH 2 , Cl, Br, , H, , etc.). These compounds are not as widely available as their perfluorinated congeners.…”

Section: Introductionmentioning

confidence: 99%

One-Pot Route to X-perfluoroarenes (X = Br, I) Based on Fe^III-Assisted C–F Functionalization and Utilization of These Arenes as Building Blocks for Crystal Engineering Involving Halogen Bonding

Rozhkov

Eliseeva

Baykov

et al. 2020

Crystal Growth & Design

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Perfluorinated arenes (benzene F derivatives, diphenyl F , naphthalene F ) were converted into X-perfluoroarenes (X = Br, I) via the developed one-pot protocol based on [Fe-(acetylacetonate) 3 ]-assisted C−F functionalization. The syntheses proceed under mild conditions and employ readily available perfluorinated arenes, which are treated with EtMgBr followed by addition of X 2 /[Fe(acetylacetonate) 3 ] (0.8 mol %); yields range from good to moderate. The σ-hole donor properties of the obtained mono-and di-X-perfluoroarenes and the significance of these species for halogen-bonding-based crystal engineering was illustrated in a series of postsynthetic experiments, all supported by density functional theory (DFT) energy calculations, molecular electrostatic potential (MEP) surface analysis, and the quantum theory of atoms in molecules (QTAIM). These include (i) a solid-state X-ray diffraction study of X-perfluoroarene self-association (dimerization) via iodine σ-holeelectron belt interactions (three X-ray structures) and (ii) verification of X-perfluoroarene σ-hole donor abilities by their interactions with iodides acting as external σ-hole acceptors (five X-ray structures); a Hirshfeld surface analysis was performed for all eight structures.

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Section: Introductionmentioning

confidence: 99%

One-Pot Route to X-perfluoroarenes (X = Br, I) Based on Fe^III-Assisted C–F Functionalization and Utilization of These Arenes as Building Blocks for Crystal Engineering Involving Halogen Bonding

Rozhkov

Eliseeva

Baykov

et al. 2020

Crystal Growth & Design

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“…Figure shows the 2D NMR ( 19 F− 19 F) COSY spectrum of PNB. There is a characteristically large coupling between peri -fluorines in PNB ( 4 J F8 - F1 = 73 Hz, 4 J F5 - F4 = 17 Hz) as in other polyfluoronaphthalenes …”

Section: Resultsmentioning

confidence: 99%

“…In comparing MePNB - to PNB, position F-6, which is pseudo- para relative to the B position, is displaced most upfield in 19 F NMR relative to the other fluorine nuclei in MePNB - (e.g., 7.52 ppm upfield in 6 and 11.36 ppm upfield in 8 versus δ F-6 in neutral PNB). It has been reported in several cases that the “pseudo- para ” site 6 is the most reactive site in heptafluoro-2-naphthyllithium, 2-methoxyheptafluoronaphthalene, and 2-methylthioheptafluoronaphthalene …”

Section: Resultsmentioning

confidence: 99%

New Organo-Lewis Acids. Tris(β-perfluoronaphthyl)borane (PNB) as a Highly Active Cocatalyst for Metallocene-Mediated Ziegler−Natta α-Olefin Polymerization

Marks

1998

Organometallics

102

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Tris(β-perfluoronaphthyl)borane (B(C10F7)3, PNB) is synthesized from β-perfluoronaphthyllithium and BCl3 to serve as a new strong organo-Lewis acid cocatalyst. PNB efficiently activates a variety of group 4 dimethyl complexes to form highly active homogeneous Ziegler−Natta olefin polymerization catalysts. Reaction of PNB with rac-Me2Si(Ind)2ZrMe2 and CGCMMe2 (M = Zr, Ti; CGC = Me2Si(η5-Me4C5)( t BuN)) (1:1 molar ratio) rapidly produces the base-free cationic complexes rac-Me2Si(Ind)2ZrMe+MePNB- (1) and CGCMMe+MePNB- (M = Zr, 2; Ti, 3), respectively. The μ-methyl dinuclear cationic complex [(CGCTiMe)2(μ-Me)]+MePNB- (4) is formed when a 2:1 CGCTiMe2:PNB stoichiometry is employed. In the case of group 4 dimethyl zirconocenes, L2ZrMe2 (L = η5-C5H5, Cp; η5-1,2-Me2C5H3, Cp‘‘), reaction in a 1:1 metallocene:PNB ratio affords cationic complexes L2ZrMe+MePNB- (L = Cp, 5; Cp‘‘, 6), while the reaction with a 1:2 molar ratio affords dinuclear μ-methyl cationic complexes [(L2ZrMe)2(μ-Me)]+MePNB- (L = Cp, 7; Cp‘‘, 8). In both reactions, μ-F dinuclear cationic complexes [(L2ZrMe)2(μ-F)]+MePNB- (L = Cp, 9; Cp‘‘, 10) are formed as byproducts. (C6F5)3BNCCH3 and PNBNCCH3 were synthesized and characterized. Analysis of the PNBNCCH3 + B(C6F5)3 ⇌ (C6F5)3BNCCH3 + PNB equilibrium yields ΔH° = +0.7(2) kcal/mol and ΔS° = +4.3(5) eu, suggesting PNB has somewhat higher Lewis acidity and is sterically more encumbered than B(C6F5)3. Solution ν(CN) values for PNBNCCH3 and (C6F5)3BNCCH3 are 2365.3 and 2366.5 cm-1, respectively, which indicate strong Lewis acidity. PBBNCCH3 cannot be detected in the reaction of (C6F5)3BNCCH3 with PBB [PBB = tris(2,2‘,2‘‘-perfluorobipheny)lborane] over prolonged periods at 60 °C. In ethylene polymerization, PNB-derived cationic complexes 5, 6, 7, and 8 have catalytic activities similar to the B(C6F5)3-derived analogues, while 2 and 3 have substantially higher activities. In propylene polymerization, catalyst 1 has higher activity than the B(C6F5)3 analogue. In the case of ethylene and 1-hexene copolymerization, PNB-derived cationic complex 3 exhibits higher polymerization activity with similar 1-hexene incorporation versus the B(C6F5)3-derived cationic complex. In large-scale batch copolymerizations of ethylene and 1-octene mediated by CGCTiMe2, the PNB-based catalytic systems exhibit approximately twice the activity of the B(C6F5)3-based systems.

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ChemInform Abstract: POLYCYCLIC FLUOROAROMATIC COMPOUNDS. PART 10. NUCLEOPHILIC REPLACEMENT OF FLUORINE IN HEPTAFLUORO‐2‐NAPHTHYLLITHIUM

Burdon¹,

Gill²,

Parsons³

1981

Chemischer Informationsdienst

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Polycyclic fluoro-aromatic compounds. Part 10. Nucleophilic replacement of fluorine in heptafluoro-2-naphthyl-lithium

Cited by 12 publications

References 0 publications

One-Pot Route to X-perfluoroarenes (X = Br, I) Based on Fe^III-Assisted C–F Functionalization and Utilization of These Arenes as Building Blocks for Crystal Engineering Involving Halogen Bonding

One-Pot Route to X-perfluoroarenes (X = Br, I) Based on Fe^III-Assisted C–F Functionalization and Utilization of These Arenes as Building Blocks for Crystal Engineering Involving Halogen Bonding

New Organo-Lewis Acids. Tris(β-perfluoronaphthyl)borane (PNB) as a Highly Active Cocatalyst for Metallocene-Mediated Ziegler−Natta α-Olefin Polymerization

ChemInform Abstract: POLYCYCLIC FLUOROAROMATIC COMPOUNDS. PART 10. NUCLEOPHILIC REPLACEMENT OF FLUORINE IN HEPTAFLUORO‐2‐NAPHTHYLLITHIUM

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Polycyclic fluoro-aromatic compounds. Part 10. Nucleophilic replacement of fluorine in heptafluoro-2-naphthyl-lithium

Cited by 12 publications

References 0 publications

One-Pot Route to X-perfluoroarenes (X = Br, I) Based on FeIII-Assisted C–F Functionalization and Utilization of These Arenes as Building Blocks for Crystal Engineering Involving Halogen Bonding

One-Pot Route to X-perfluoroarenes (X = Br, I) Based on FeIII-Assisted C–F Functionalization and Utilization of These Arenes as Building Blocks for Crystal Engineering Involving Halogen Bonding

New Organo-Lewis Acids. Tris(β-perfluoronaphthyl)borane (PNB) as a Highly Active Cocatalyst for Metallocene-Mediated Ziegler−Natta α-Olefin Polymerization

ChemInform Abstract: POLYCYCLIC FLUOROAROMATIC COMPOUNDS. PART 10. NUCLEOPHILIC REPLACEMENT OF FLUORINE IN HEPTAFLUORO‐2‐NAPHTHYLLITHIUM

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One-Pot Route to X-perfluoroarenes (X = Br, I) Based on Fe^III-Assisted C–F Functionalization and Utilization of These Arenes as Building Blocks for Crystal Engineering Involving Halogen Bonding

One-Pot Route to X-perfluoroarenes (X = Br, I) Based on Fe^III-Assisted C–F Functionalization and Utilization of These Arenes as Building Blocks for Crystal Engineering Involving Halogen Bonding