Matrix reactions of fluorohalomethanes with alkali metals. Infrared spectrum and bonding in the monofluoromethyl radical

Raymond, James I.; Andrews, Lester

doi:10.1021/j100690a007

Cited by 36 publications

(29 citation statements)

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“…Absorptions of H 2 CF, HCF, and CF radicals, fragments of methyl fluoride, result from photolysis by the laser-ablation plume. [13,14] These absorptions are common to previous investigations with methyl fluoride. [1][2][3] Group I: Following our investigations with Group 4 metal atoms and CH 3 F, we expected metal insertion into the CÀF bond to form the methyl molybdenum fluoride [CH 3 ÀMoF].…”

Section: Resultssupporting

confidence: 68%

“…[13,14] These absorptions are common to previous investigations with methyl fluoride. [1][2][3] Group I: Following our investigations with Group 4 metal atoms and CH 3 Group II: The IR spectra in Figures 1, 2, and 3 show that the compound responsible for group II is formed originally in a relatively large amount in the reaction of methyl fluo- CH 3 F in Ar co-deposited for 1 h, b) after broad-band irradiation with a filter (l > 420 nm) for 20 min, c) after broad-band irradiation with a UV-transmitting filter (240 < l < 380 nm), d) after l > 420 nm irradiation, e) after 240-380 nm irradiation, f) after l > 420 nm irradiation, and g) after annealing to 26 K. I, II, or III stands for the product band group.…”

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confidence: 67%

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[CH₃MoF], [CH₂MoHF], and [CHMoH₂F] Formed by Reaction of Laser‐Ablated Molybdenum Atoms with Methyl Fluoride: Persistent Photoreversible Interconversion through α‐Hydrogen Migration and Agostic Interaction

Cho

Andrews

2005

Chemistry A European J

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Simple molybdenum methyl, carbene, and carbyne complexes, [CH3--MoF], [CH2=MoHF], and [CH[triple chemical bond]MoH(2)F], were formed by the reaction of laser-ablated molybdenum atoms with methyl fluoride and isolated in an argon matrix. These molecules provide a persistent photoreversible system through alpha-hydrogen migration between the carbon and metal atoms: The methyl and carbene complexes are produced by applying UV irradiation (240-380 nm) while the carbyne complex is depleted, and the process reverses on irradiation with visible light (lambda>420 nm). An absorption at 589.3 cm(-1) is attributed to the Mo--F stretching mode of [CH3--MoF], which is in fact the most stable of the plausible products. Density functional theory calculations show that one of the alpha-hydrogen atoms of the carbene complex is considerably bent toward the metal atom (angle-spherical HCMo=84.5 degrees ), which provides evidence of a strong agostic interaction in the triplet ground state. The calculated C[triple chemical bond]Mo bond length in the carbyne is in the range of triple-bond values in methylidyne complexes.

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Section: Resultssupporting

confidence: 68%

supporting

confidence: 67%

[CH₃MoF], [CH₂MoHF], and [CHMoH₂F] Formed by Reaction of Laser‐Ablated Molybdenum Atoms with Methyl Fluoride: Persistent Photoreversible Interconversion through α‐Hydrogen Migration and Agostic Interaction

Cho

Andrews

2005

Chemistry A European J

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“…26 The generation of a monofluoromethyl radical is practically unknown, with only one report made on its characterization by a matrix reaction of bromofluoromethane with alkali metals, without demonstration of synthetic applicability. 27 As fluoroacetic acid (CH 2 F-CO 2 H) cannot generate radicals under standard Minisci conditions, a practical CH 2 F radical precursor and its application to synthetic chemistry is required; MFMS ( D ) is a new reagent devised for this purpose.…”

mentioning

confidence: 99%

Practical and innate carbon–hydrogen functionalization of heterocycles

Fujiwara

Dixon

O’Hara

et al. 2012

Nature

830

397

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Nitrogen-rich heterocyclic compounds have had a profound impact on human health, as these chemical motifs are found in a large number of drugs used to combat a broad range of diseases and pathophysiological conditions. Advances in transition metal-mediated cross-coupling have simplified the synthesis of such molecules; however, the development of practical and selective C–H functionalization methods that do not rely upon prefunctionalized starting materials is an underdeveloped area.1–9 Paradoxically, the innate properties of heterocycles that make them so desirable for biological applications render them challenging substrates for direct chemical functionalization, such as limited solubility, functional group incompatibilities, and reagent/catalyst deactivation. Herein we report that zinc sulfinate salts9 can be used to transfer alkyl radicals to heterocycles, allowing for a mild, direct and operationally simple formation of medicinally relevant C–C bonds while reacting in an orthogonal fashion to other innate C–H functionalization methods (Minisci, borono-Minisci, electrophilic aromatic substitution, transition metal-mediated C–H insertion, C–H deprotonation).2–7,9 A toolkit of these reagents was prepared and reacted across a wide range of heterocycles (natural products, drugs, building blocks) without recourse to protecting group chemistry, and can even be employed in a tandem fashion in a single pot in the presence of water and air.

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“…194 Subsequent work has also described the use of sulfonium ylides for the monofluoromethylation of 2-aryl-substituted and 2-alkyl-substituted malonates. 195 Although the CH2F radical was first observed and characterized in 1971, 199 9E). 188 Similarly, a ruthenium photoredox catalyst can be used for generating monofluoromethyl radicals from monofluoromethyl sulfones for radical additions into isocyanides.…”

Section: [H2] Monofluoromethylationmentioning

confidence: 99%

Contemporary synthetic strategies in organofluorine chemistry

Britton

Gouverneur

Lin

et al. 2021

Nat Rev Methods Primers

189

115

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At this stage, I've edited the manuscript for brevity and clarity. Queries are meant to draw your attention to edits, inconsistencies or issues that are unclear. If we just ask you to confirm edits are correct, a simple yes/ok between the brackets will do [Au:OK? Is this what you meant? Edits OK? yes]. If questions are asked, please rephrase/update the manuscript text when addressing queries, so that the message is conveyed to the reader (please do not just type your answer to our query unless it is unclear).As the reviewers noted, the manuscript is in very good shape and most comments and edits are fairly minor. However, there is an outstanding issue that must be addressed before we go forward. Figures 7 and 8 are currently referred to in the text in an alternating fashion (e.g. Figure 7A, 8A, 7B, 8B). This is against our style and might make that part of the manuscript difficult to follow for the reader owing to the need to refer to multiple figures at a time while reading the text. To clarify this issue, I recommend restructuring these figures. To do this, can you provide new chemdraw/PDFs with amended figures, including the following amendments: a. Merge Figures 7A and 8A to create a new 'Figure 7' that shows the methods of introducing CF2H at sp3-carbons. b. Merge figures 7B and 8B to make a new figure 8 that shows the main protocols of introducing CF2H at heteroaromatic carbons. 7C could be shown in it's own small figure (Figure 9) or could be added as panel B in the new figure 8. c. Amend the figure legends accordingly Apologies for another figure change but this is essential to keep the figure callouts in style and I think it will make the figures much easier for the reader to follow. I've asked the art editor to delay redrawing these particular figures until we receive these updated chemdraws/PDFs. If there are any issues with this change, please do let me know as soon as possible and we can discuss further.

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Matrix reactions of fluorohalomethanes with alkali metals. Infrared spectrum and bonding in the monofluoromethyl radical

Cited by 36 publications

References 4 publications

[CH₃MoF], [CH₂MoHF], and [CHMoH₂F] Formed by Reaction of Laser‐Ablated Molybdenum Atoms with Methyl Fluoride: Persistent Photoreversible Interconversion through α‐Hydrogen Migration and Agostic Interaction

[CH₃MoF], [CH₂MoHF], and [CHMoH₂F] Formed by Reaction of Laser‐Ablated Molybdenum Atoms with Methyl Fluoride: Persistent Photoreversible Interconversion through α‐Hydrogen Migration and Agostic Interaction

Practical and innate carbon–hydrogen functionalization of heterocycles

Contemporary synthetic strategies in organofluorine chemistry

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Matrix reactions of fluorohalomethanes with alkali metals. Infrared spectrum and bonding in the monofluoromethyl radical

Cited by 36 publications

References 4 publications

[CH3MoF], [CH2MoHF], and [CHMoH2F] Formed by Reaction of Laser‐Ablated Molybdenum Atoms with Methyl Fluoride: Persistent Photoreversible Interconversion through α‐Hydrogen Migration and Agostic Interaction

[CH3MoF], [CH2MoHF], and [CHMoH2F] Formed by Reaction of Laser‐Ablated Molybdenum Atoms with Methyl Fluoride: Persistent Photoreversible Interconversion through α‐Hydrogen Migration and Agostic Interaction

Practical and innate carbon–hydrogen functionalization of heterocycles

Contemporary synthetic strategies in organofluorine chemistry

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Product

Resources

About

[CH₃MoF], [CH₂MoHF], and [CHMoH₂F] Formed by Reaction of Laser‐Ablated Molybdenum Atoms with Methyl Fluoride: Persistent Photoreversible Interconversion through α‐Hydrogen Migration and Agostic Interaction

[CH₃MoF], [CH₂MoHF], and [CHMoH₂F] Formed by Reaction of Laser‐Ablated Molybdenum Atoms with Methyl Fluoride: Persistent Photoreversible Interconversion through α‐Hydrogen Migration and Agostic Interaction