Oxidation reactions of a nucleophilic palladium carbene: mono and bi-radical carbenes

Cui, Peng; Hoffbauer, Melissa R.; Vyushkova, Mariya; Iluc, Vlad M.

doi:10.1039/c9dt00585d

Cited by 10 publications

(2 citation statements)

References 48 publications

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“…We have been studying group 10 metal carbenes supported by [PC(sp 2 )P] ((bis[2-(di-isopropylphosphino)phenyl]methane)) and discovered new reactivity patterns for late transition metal carbenes. − The rich reactivity observed for these carbenes − prompted us to expand our studies to iron − and probe the reactivity of the corresponding compounds. Herein, we report the synthesis of [{PC(sp 2 )P}Fe(N 2 )(PMe 3 )] ( 1-N 2 -PMe 3 ) and its unprecedented [2+2] reactivity with alkynes to produce η 3 -vinyl carbene iron complexes, [{PC(C Ph C(sp 2 ) Ph }Fe(L)] ( 2-L , L = N 2 , PMe 3 , Figure E).…”

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[2+2] Cycloadditions with an Iron Carbene: A Critical Step in Enyne Metathesis

Hoffbauer

Iluc

2021

J. Am. Chem. Soc.

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Ruthenium carbenes, famously used in olefin metathesis, have impacted numerous research areas, ranging from synthesis to materials and biology. Although in the same group as ruthenium, iron carbenes showing similar reaction patterns have not been reported. Such targets are of high interest because the use of a sustainable metal would lead to a decreased cost, toxicity, and environmental impact of the corresponding compounds. Herein, we report the synthesis of an iron carbene complex, [{PC(sp2)P}Fe(N2)(PMe3)] ([PC(sp2)P] = (bis[2-(di-isopropylphosphino)phenyl]methylene), which is capable of performing [2+2] cycloaddition reactions in the presence of alkynes. Specifically, η3-vinyl carbenes are formed stoichiometrically through a [2+2] cycloaddition between the alkyne and the metal carbene. Additional reactivity of the η3-vinyl carbenes with alkynes yields a second insertion product containing a new iron carbene moiety.

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[2+2] Cycloadditions with an Iron Carbene: A Critical Step in Enyne Metathesis

Hoffbauer

Iluc

2021

J. Am. Chem. Soc.

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“…PC carbene P pincer complexes have also displayed other unique metal–ligand cooperativities with potential applications in bond activation and catalysis. For instance, the ability to stabilize electrophilic, nucleophilic, and radical central carbene donors and to easily convert between these states, allows the carbene position to act as an auxiliary reactive site to the metal center . The MC connection has been shown to capture π-donor small molecules, such as alkynes, nitriles, alkenes, and carbonyls, through formal [2 + 2] addition.…”

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Catalytic Deoxygenation of Amine and Pyridine N-Oxides Using Rhodium PC_carbeneP Pincer Complexes

et al. 2020

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Rhodium PCcarbeneP pincer complexes 1-L (L = PPh3, PPh2(C6F5), PCy3) readily facilitate deoxygenation of amine and pyridine N-oxides. The resulting complexes exhibit η2-CO coordination of the resulting keto POP pincer ligand. These η2-CO linkages in the metalloepoxide complexes are readily reduced by isopropyl alcohol and various benzylic alcohols. Thus, efficient catalytic deoxygenation of amine and pyridine N-oxides is possible using complexes 1-L and isopropyl alcohol. This represents a pioneering example of PCcarbeneP pincer complexes being used as catalysts for catalytic deoxygenation.

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Access to and Reactivity of Fe⁰, Fe^−I, Fe^I, and Fe^II PC_carbeneP Pincer Complexes

et al. 2021

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Despite their promising metal–ligand cooperative reactivity, PCcarbeneP pincer ligands are rarely reported for first‐row transition‐metal centres. Using a dehydration methodology, we report access to an Fe0 PCcarbeneP pincer complex (1) that proceeds via an isolated α‐hydroxylalkyl hydrido complex (3). Reversible carbonyl migration to the carbene position in 1 is found to allow coordination chemistry and E−H bond addition (E=H, B, Cl) across the iron–carbene linkage, representing a unique mechanism for metal–ligand cooperativity. The PCcarbeneP pincer ligand is also found to stabilize formal FeII, FeI, and Fe−I oxidation states, as demonstrated with synthesis and characterization of the complexes [11‐X][BArF20] (X=Br, I), 12, and K[13]. Compound K[13] is found to be highly reactive, and abstracts hydrogen from a range of aliphatic C−H sources. Computational analysis by DFT suggests that the formal FeI and Fe−I complexes contain significant carbene radical character. The ability of the PCcarbeneP ligand scaffold to partake in metal–ligand cooperativity and to support a range of iron oxidation states renders it as potentially useful in many catalytic applications.

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Oxidation reactions of a nucleophilic palladium carbene: mono and bi-radical carbenes

Abstract: A series of mono and bi-radical carbenes.

Cited by 10 publications

References 48 publications

[2+2] Cycloadditions with an Iron Carbene: A Critical Step in Enyne Metathesis

[2+2] Cycloadditions with an Iron Carbene: A Critical Step in Enyne Metathesis

Catalytic Deoxygenation of Amine and Pyridine N-Oxides Using Rhodium PC_carbeneP Pincer Complexes

Access to and Reactivity of Fe⁰, Fe^−I, Fe^I, and Fe^II PC_carbeneP Pincer Complexes

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Oxidation reactions of a nucleophilic palladium carbene: mono and bi-radical carbenes

Abstract: A series of mono and bi-radical carbenes.

Cited by 10 publications

References 48 publications

[2+2] Cycloadditions with an Iron Carbene: A Critical Step in Enyne Metathesis

[2+2] Cycloadditions with an Iron Carbene: A Critical Step in Enyne Metathesis

Catalytic Deoxygenation of Amine and Pyridine N-Oxides Using Rhodium PCcarbeneP Pincer Complexes

Access to and Reactivity of Fe0, Fe−I, FeI, and FeII PCcarbeneP Pincer Complexes

Contact Info

Product

Resources

About

Catalytic Deoxygenation of Amine and Pyridine N-Oxides Using Rhodium PC_carbeneP Pincer Complexes

Access to and Reactivity of Fe⁰, Fe^−I, Fe^I, and Fe^II PC_carbeneP Pincer Complexes