One‐Electron Oxidation of [M(PtBu3)2] (M=Pd, Pt): Isolation of Monomeric [Pd(PtBu3)2]+ and Redox‐Promoted C−H Bond Cyclometalation

Troadec, Thibault; Tan, Sze‐yin; Wedge, Christopher J.; Rourke, Jonathan P.; Unwin, Patrick R.; Chaplin, Adrian B.

doi:10.1002/anie.201511467

Cited by 28 publications

(28 citation statements)

References 53 publications

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“…15 The same reactivity was noticed upon dissolving compounds 1 or 2 in tetrahydrofuran. An identical transformation was latterly reported using a ferrocenium salt as the one-electron oxidant, 16 a role presumably played by the silver salt in the compounds reported herein.…”

supporting

confidence: 84%

Cooperative activation of X–H (X = H, C, O, N) bonds by a Pt(0)/Ag(i) metal-only Lewis pair

2019

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supporting

confidence: 84%

Cooperative activation of X–H (X = H, C, O, N) bonds by a Pt(0)/Ag(i) metal-only Lewis pair

2019

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“…21 It has been subsequently employed to study the redox behaviour of a range of reactive transition metal complexes. 22,23 Eisenstein, Faller, Crabtree and colleagues identified FB as a "less coordinating and less oxidising" solvent compared to CH 2 Cl 2 during the synthesis of low-coordinate iridium complexes in 2002. 24 16 is a useful solvent choice for this and other reactions, it is much is more susceptible to C-F bond activation than FB and 1,2-DiFB.…”

Section: Fluorobenzenes As Solventsmentioning

confidence: 99%

Organometallic chemistry using partially fluorinated benzenes

2017

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Fluorobenzenes, in particular fluorobenzene (FB) and 1,2-difluorobenzene (1,2-DiFB), are increasingly becoming recognised as versatile solvents for conducting organometallic chemistry and transition-metal-based catalysis. The presence of fluorine substituents reduces the ability to donate π-electron density from the arene and consequently fluorobenzenes generally bind weakly to metal centres, allowing them to be used as essentially non-coordinating solvents or as readily displaced ligands. In this context, examples of well-defined complexes of fluorobenzenes are discussed, including trends in binding strength with increasing fluorination and different substitution patterns. Compared to more highly fluorinated benzenes, FB and 1,2-DiFB typically demonstrate greater chemical inertness, however, C-H and C-F bond activation reactions can be induced using appropriately reactive transition metal complexes. Such reactions are surveyed, including catalytic examples, not only to provide perspective for the use of FB and 1,2-DiFB as innocent solvent media, but also to highlight opportunities for their exploitation in contemporary organic synthesis.

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“…The identification of this species supports the proposed formation of Pd(I) intermediates from Pd(0)-trialkylphopshine complexes. 46 …”

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confidence: 99%

Palladium-Catalyzed Cross Coupling of Secondary and Tertiary Alkyl Bromides with a Nitrogen Nucleophile

2016

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We report a new class of catalytic reaction: the thermal substitution of a secondary and or tertiary alkyl halide with a nitrogen nucleophile. The alkylation of a nitrogen nucleophile with an alkyl halide is a classical method for the construction of C–N bonds, but traditional substitution reactions are challenging to achieve with a secondary and or tertiary alkyl electrophile due to competing elimination reactions. A catalytic process could address this limitation, but thermal, catalytic coupling of alkyl halides with a nitrogen nucleophile and any type of catalytic coupling of an unactivated tertiary alkyl halide with a nitrogen nucleophile are unknown. We report the coupling of unactivated secondary and tertiary alkyl bromides with benzophenone imines to produce protected primary amines in the presence of palladium ligated by the hindered trialkylphosphine Cy2t-BuP. Mechanistic studies indicate that this amination of alkyl halides occurs by a reversible reaction to form a free alkyl radical.

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One‐Electron Oxidation of [M(P^tBu₃)₂] (M=Pd, Pt): Isolation of Monomeric [Pd(P^tBu₃)₂]⁺ and Redox‐Promoted C−H Bond Cyclometalation

Cited by 28 publications

References 53 publications

Cooperative activation of X–H (X = H, C, O, N) bonds by a Pt(0)/Ag(i) metal-only Lewis pair

Cooperative activation of X–H (X = H, C, O, N) bonds by a Pt(0)/Ag(i) metal-only Lewis pair

Organometallic chemistry using partially fluorinated benzenes

Palladium-Catalyzed Cross Coupling of Secondary and Tertiary Alkyl Bromides with a Nitrogen Nucleophile

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