Selektive Übertragung eines Stickstoffatoms im [CeON]<sup>+</sup>/CH<sub>4</sub>‐System durch hocheffizientes Intersystem Crossing

C−H amination and amidation by catalytic nitrene transfer are well‐established and typically proceed via electrophilic attack of nitrenoid intermediates. In contrast, the insertion of (formal) terminal nitride ligands into C−H bonds is much less developed and catalytic nitrogen atom transfer remains unknown. We here report the synthesis of a formal terminal nitride complex of palladium. Photocrystallographic, magnetic, and computational characterization support the assignment as an authentic metallonitrene (Pd−N) with a diradical nitrogen ligand that is singly bonded to PdII. Despite the subvalent nitrene character, selective C−H insertion with aldehydes follows nucleophilic selectivity. Transamidation of the benzamide product is enabled by reaction with N3SiMe3. Based on these results, a photocatalytic protocol for aldehyde C−H trimethylsilylamidation was developed that exhibits inverted, nucleophilic selectivity as compared to typical nitrene transfer catalysis. This first example of catalytic C−H nitrogen atom transfer offers facile access to primary amides after deprotection.

show abstract

Nitrogen Atom Transfer Catalysis by Metallonitrene C−H Insertion: Photocatalytic Amidation of Aldehydes

Schmidt-Räntsch

Verplancke

Lienert

et al. 2022

Angewandte Chemie

View full text Add to dashboard Cite

show abstract

Nitrogen Atom Transfer Catalysis by Metallonitrene C−H Insertion: Photocatalytic Amidation of Aldehydes

et al. 2022

View full text Add to dashboard Cite

show abstract

Conversion of CH₄ Catalyzed by Gas Phase Ions Containing Metals

Yang

Zhao

2022

Chemistry A European J

View full text Add to dashboard Cite

Methane is an abundant and cheap feedstock to produce valuable chemicals. The catalytic reaction of methane conversion generally requires the participation of multiple molecules (such as two or three CH4 molecules, O2, CO2, etc.). Such complex process includes the cleavage of original chemical bonds, formation of new chemical bonds, and desorption of products. The gas phase study provides a unique arena to gain molecular‐level insights into the detailed mechanisms of bond‐breaking and bond‐forming involved in complicated catalytic reactions. In this Review, we introduce the methane conversion catalyzed by gas phase ions containing metals and three topics will be discussed: (1) the direct coupling of methane molecules, (2) the conversion of CH4 with O2, O3 and N2O, and (3) the conversion of CH4 with CO2 and H2O. The obtained mechanistic aspects may provide new clues for rational design of better‐performing catalysts for conversion of methane to value‐added products.

show abstract

scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.

Contact Info

customersupport@researchsolutions.com

10624 S. Eastern Ave., Ste. A-614

Henderson, NV 89052, USA

This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.

Blog Terms and Conditions API Terms Privacy Policy Contact Cookie Preferences Do Not Sell or Share My Personal Information

Made with 💙 for researchers

Part of the Research Solutions Family.

Selektive Übertragung eines Stickstoffatoms im [CeON]⁺/CH₄‐System durch hocheffizientes Intersystem Crossing

Cited by 4 publications

References 58 publications

Nitrogen Atom Transfer Catalysis by Metallonitrene C−H Insertion: Photocatalytic Amidation of Aldehydes

Nitrogen Atom Transfer Catalysis by Metallonitrene C−H Insertion: Photocatalytic Amidation of Aldehydes

Nitrogen Atom Transfer Catalysis by Metallonitrene C−H Insertion: Photocatalytic Amidation of Aldehydes

Conversion of CH₄ Catalyzed by Gas Phase Ions Containing Metals

Contact Info

Product

Resources

About

Selektive Übertragung eines Stickstoffatoms im [CeON]+/CH4‐System durch hocheffizientes Intersystem Crossing

Cited by 4 publications

References 58 publications

Nitrogen Atom Transfer Catalysis by Metallonitrene C−H Insertion: Photocatalytic Amidation of Aldehydes

Nitrogen Atom Transfer Catalysis by Metallonitrene C−H Insertion: Photocatalytic Amidation of Aldehydes

Nitrogen Atom Transfer Catalysis by Metallonitrene C−H Insertion: Photocatalytic Amidation of Aldehydes

Conversion of CH4 Catalyzed by Gas Phase Ions Containing Metals

Contact Info

Product

Resources

About

Selektive Übertragung eines Stickstoffatoms im [CeON]⁺/CH₄‐System durch hocheffizientes Intersystem Crossing

Conversion of CH₄ Catalyzed by Gas Phase Ions Containing Metals