Complex dependent regioselectivity in the nucleophilic substitution of fluorine of a coordinated tetrafluoropyridyl N-heterocycle carbene

Pachal, Sam R.; Saunders, Graham C.; Weston, Jessica K.

doi:10.1016/j.ica.2012.09.019

Cited by 7 publications

(11 citation statements)

References 31 publications

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“…We have previously identified intramolecular dehydrofluorinative carbon-carbon coupling as a rapid, highyielding route to η 5 ,κP-cyclopentadienyl-phospshine complexes of rhodium and 5,6 iridium. 7 The cationic complexes 9 Here we report the formation of a rhodium complex of an η 5 ,κC-cyclopentadienyl-NHC ligand by an intramolecular addition reaction.…”

Section: Supporting Information Placeholdermentioning

confidence: 99%

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Tethering of Pentamethylcyclopentadienyl and N-Heterocycle Stabilized Carbene Ligands by Intramolecular 1,4-Addition to a Polyfluorophenyl Substituent

et al. 2018

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Section: Supporting Information Placeholdermentioning

confidence: 99%

“…7 The cationic complexes on treatment with base. 9 Here we report the formation of a rhodium complex of an η 5 ,κC-cyclopentadienyl-NHC ligand by an intramolecular addition reaction. The NMR spectroscopic and mass spectral data are entirely consistent with the structure of 2 (see the Supporting Information).…”

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confidence: 92%

Tethering of Pentamethylcyclopentadienyl and N-Heterocycle Stabilized Carbene Ligands by Intramolecular 1,4-Addition to a Polyfluorophenyl Substituent

et al. 2018

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“…undergo undesired reactions in their syntheses [13], and the sole example of an imidazolium salt that is a precursor to 1-polyfluoroarylmethyl-3-arylimidazol-2-ylidene (III) does not possess ─ stacking [7]. Consequently a structural study of ( 5 -pentamethylcyclopentadienyl)rhodium and iridium complexes of 1-(2,3,4,5,6-pentafluorophenylmethyl)-3-benzylimidazol-2-ylidene and its analogue 1- undertaken.…”

Section: Introductionmentioning

confidence: 99%

Arene-polyfluoroarene π-π stacking between N-heterocyclic carbene ligands of pentamethylcyclopentadienyl group 9 metal complexes

Lockley

Marr

Saunders

et al. 2019

Journal of Fluorine Chemistry

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Highlights  The crystal structures of the dichloromethane solvates of ( 5pentamethylcyclopentadienyl)rhodium(κC-1-(4-trifluoromethyl-2,3,5,6-the phenyl and trifluoromethyltetrafluorophenyl rings of molecules in a direction perpendicular to the columns and hydrogen bonding between the complex molecules. In contrast those of 1a and 1b display intermolecular lone pair- interactions in the same direction as the hydrogen bonding between the complex molecules. DFT calculations reveal that the - stacking and lone pair- interactions are of approximately the same energy. The difference in the structures arises from the steric requirements of the trifluoromethyl group.

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“… 13 Attack on a η 5 -pentamethylcyclopentadienyl rhodium(III) complex occurred at the less activated position, meta to the ring nitrogen atom, of a tetrafluoropyridyl substituent of a coordinated N-heterocyclic carbene. 14 …”

Section: Introductionmentioning

confidence: 99%

Photochemical Reactions of Fluorinated Pyridines at Half-Sandwich Rhodium Complexes: Competing Pathways of Reaction

et al. 2013

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Irradiation of CpRh(PMe3)(C2H4) (1; Cp = η5-C5H5) in the presence of pentafluoropyridine in hexane solution at low temperature yields an isolable η2-C,C-coordinated pentafluoropyridine complex, CpRh(PMe3)(η2-C,C-C5NF4) (2). The molecular structure of 2 was determined by single-crystal X-ray diffraction, showing coordination by C3–C4, unlike previous structures of pentafluoropyridine complexes that show N-coordination. Corresponding experiments with 2,3,5,6-tetrafluoropyridine yield the C–H oxidative addition product CpRh(PMe3)(C5NF4)H (3). In contrast, UV irradiation of 1 in hexane, in the presence of 4-substituted tetrafluoropyridines C5NF4X, where X = NMe2, OMe, results in elimination of C2H4 and HF to form the metallacycles CpRh(PMe3)(κ2-C,C-CH2N(CH3)C5NF3) (4) and CpRh(PMe3)(κ2-C,C-CH2OC5NF3) (5), respectively. The X-ray structure of 4 shows a planar RhCCNC-five-membered ring. Complexes 2–5 may also be formed by thermal reaction of CpRh(PMe3)(Ph)H with the respective pyridines at 50 °C.

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Complex dependent regioselectivity in the nucleophilic substitution of fluorine of a coordinated tetrafluoropyridyl N-heterocycle carbene

Cited by 7 publications

References 31 publications

Tethering of Pentamethylcyclopentadienyl and N-Heterocycle Stabilized Carbene Ligands by Intramolecular 1,4-Addition to a Polyfluorophenyl Substituent

Tethering of Pentamethylcyclopentadienyl and N-Heterocycle Stabilized Carbene Ligands by Intramolecular 1,4-Addition to a Polyfluorophenyl Substituent

Arene-polyfluoroarene π-π stacking between N-heterocyclic carbene ligands of pentamethylcyclopentadienyl group 9 metal complexes

Photochemical Reactions of Fluorinated Pyridines at Half-Sandwich Rhodium Complexes: Competing Pathways of Reaction

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