Coupling dinitrogen and hydrocarbons through aryl migration

Sean F. McWilliams, Daniël L. J. Broere, Connor J. V. Halliday, Samuel M. Bhutto, Brandon Q. Mercado and Patrick L. Holland ()
Additional contact information
Sean F. McWilliams: Yale University
Daniël L. J. Broere: Yale University
Connor J. V. Halliday: University of Edinburgh
Samuel M. Bhutto: Yale University
Brandon Q. Mercado: Yale University
Patrick L. Holland: Yale University

Nature, 2020, vol. 584, issue 7820, 221-226

Abstract: Abstract The activation of abundant molecules such as hydrocarbons and atmospheric nitrogen (N2) remains a challenge because these molecules are often inert. The formation of carbon–nitrogen bonds from N2 typically has required reactive organic precursors that are incompatible with the reducing conditions that promote N2 reactivity1, which has prevented catalysis. Here we report a diketiminate-supported iron system that sequentially activates benzene and N2 to form aniline derivatives. The key to this coupling reaction is the partial silylation of a reduced iron–dinitrogen complex, followed by migration of a benzene-derived aryl group to the nitrogen. Further reduction releases N2-derived aniline, and the resulting iron species can re-enter the cyclic pathway. Specifically, we show that an easily prepared diketiminate iron bromide complex2 mediates the one-pot conversion of several petroleum-derived arenes into the corresponding silylated aniline derivatives, by using a mixture of sodium powder, crown ether, trimethylsilyl bromide and N2 as the nitrogen source. Numerous compounds along the cyclic pathway are isolated and crystallographically characterized, and their reactivity supports a mechanism for sequential hydrocarbon activation and N2 functionalization. This strategy couples nitrogen atoms from N2 with abundant hydrocarbons, and maps a route towards future catalytic systems.

Date: 2020
References: Add references at CitEc
Citations: View citations in EconPapers (2)

Downloads: (external link)
https://www.nature.com/articles/s41586-020-2565-5 Abstract (text/html)
Access to the full text of the articles in this series is restricted.

Related works:
This item may be available elsewhere in EconPapers: Search for items with the same title.

Export reference: BibTeX RIS (EndNote, ProCite, RefMan) HTML/Text

Persistent link: https://EconPapers.repec.org/RePEc:nat:nature:v:584:y:2020:i:7820:d:10.1038_s41586-020-2565-5

Ordering information: This journal article can be ordered from
https://www.nature.com/

DOI: 10.1038/s41586-020-2565-5

Access Statistics for this article

Nature is currently edited by Magdalena Skipper

More articles in Nature from Nature
Bibliographic data for series maintained by Sonal Shukla () and Springer Nature Abstracting and Indexing ().