Related Experiment Video
Updated: Jun 6, 2026
08:40
Synthesis of Metal Nanoparticles Supported on Carbon Nanotube with Doped Co and N Atoms and its Catalytic Applications in Hydrogen Production
Published on: December 6, 2021
Dinitrogen cleavage and functionalization by carbon monoxide promoted by a hafnium complex
Donald J Knobloch1, Emil Lobkovsky, Paul J Chirik
1Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853, USA.
Nature Chemistry
|December 3, 2010
Summary
Researchers discovered a hafnium compound that cleaves molecular nitrogen (N(2)) using carbon monoxide (CO). This breakthrough enables direct synthesis of oxamide, an agrochemical, from these abundant feedstocks.
Area of Science:
- * Inorganic Chemistry
- * Organometallic Chemistry
- * Catalysis
Background:
- * Molecular nitrogen (N(2)) and carbon monoxide (CO) possess exceptionally strong chemical bonds, posing significant challenges for their utilization as feedstocks.
- * Developing catalytic systems for the reductive cleavage of N(2) under mild conditions (ambient temperature and pressure) is a key objective in chemistry.
- * New transformations are needed to exploit N(2) and CO for synthesizing valuable compounds.
Purpose of the Study:
- * To discover transition-metal compounds capable of promoting the six-electron reductive cleavage of N(2) at ambient conditions.
- * To develop a method for forming new nitrogen-element and carbon-carbon bonds using N(2) and CO.
- * To demonstrate the synthesis of an important agrochemical directly from N(2) and CO.
Main Methods:
- * Investigation of an organometallic hafnium compound's reactivity.
- * Reaction of the hafnium compound with molecular nitrogen (N(2)) and carbon monoxide (CO).
- * Characterization of reaction products and subsequent transformations.
Main Results:
- * The organometallic hafnium compound induced N(2) cleavage upon addition of CO.
- * Simultaneous formation of new nitrogen-carbon and carbon-carbon bonds was observed.
- * Subsequent treatment with a weak acid liberated oxamide, demonstrating direct synthesis from N(2) and CO.
Conclusions:
- * A novel catalytic system based on a hafnium compound facilitates N(2) cleavage and functionalization.
- * Carbon monoxide acts as a co-promoter in the six-electron reductive cleavage of N(2).
- * This work presents a new paradigm for N(2) utilization, enabling the synthesis of agrochemicals like oxamide from abundant feedstocks.
More Related Videos
Related Concept Videos
02:50Catalysis
The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.
01:10Aldehydes and Ketones with HCN: Cyanohydrin Formation Mechanism
Cyanohydrins are formed when cyanide nucleophiles and carbonyl compounds like aldehydes and ketones react. A strong base, the cyanide ion, catalyzes cyanohydrin formation. The ions are generated from HCN under aqueous conditions. Once the cyanide ions are generated, the first step involves the nucleophilic attack of the cyanide ions on the electrophilic carbonyl carbon. This attack shifts the π electrons from the C=O to the oxygen atom forming the alkoxide ion intermediate. The alkoxide anion...
00:54Radical Formation: Homolysis
A bond is formed between two atoms by sharing two electrons. When this bond is broken by supplying sufficient energy, either two electrons can be taken up by one atom forming ions by the cleavage called heterolysis, or the two electrons are shared by two atoms, with one each creating radicals by the cleavage called homolysis.
01:09Aldehydes and Ketones to Alkanes: Wolff–Kishner Reduction
Wolff–Kishner reduction involves converting aldehydes and ketones to alkanes using hydrazine and a base. The reaction converts a carbonyl group to a methylene group. The method was independently discovered by N. Kishner in 1911 and L. Wolff in 1912. The reduction is carried out in high-boiling solvents such as ethylene glycol and diethylene glycol because heat is required to deprotonate the N–H proton in one of the reaction steps.
01:32Aldehydes and Ketones with HCN: Cyanohydrin Formation Overview
Cyanohydrins are compounds that contain –CN and –OH groups on the same carbon atom. They are formed by the nucleophilic addition of the cyanide ions to the carbonyl group. Cyanide ions are highly basic and nucleophilic and can be generated from HCN under aqueous conditions. However, since HCN is a weak acid, the number of cyanide ions generated is very small. Hence, a small amount of base or KCN/NaCN is added to HCN to increase the concentration of the cyanide ions in the reaction mixture.
02:24Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.