Direct intramolecular carbon(sp2)-nitrogen(sp2) reductive elimination from gold(iii)

Jong Hyun Kim, R. Tyler Mertens, Amal Agarwal, Sean Parkin, Gilles Berger, Samuel G. Awuah

Research output: Contribution to journalArticlepeer-review

19 Scopus citations

Abstract

The reactivity of bidentate AuIII-Cl species, [(C^N)AuCl2], with a bisphosphine or carbon donor ligands results in reductive elimination. Combined experimental and computational investigations lead to the first evidence of a direct intramolecular C(sp2)-N(sp2) bond formation from a monomeric [(C^N)AuCl2] gold(iii) complex. We show that bidentate ligated Au(iii) systems bypass transmetallation to form C(sp2)-N(sp2) species and NHC-Au-Cl. Mechanistic investigations of the reported transformation reveal a ligand-induced reductive elimination via a key AuIII intermediate. Kinetic studies of the reaction support a second-order rate process.

Original languageEnglish
Pages (from-to)6273-6282
Number of pages10
JournalDalton Transactions
Volume48
Issue number18
DOIs
StatePublished - 2019

Bibliographical note

Publisher Copyright:
© The Royal Society of Chemistry 2019.

Funding

We are grateful to the staff and facilities at the University of Kentucky that supported this work. This study made use of the NMR facility supported by NSF (CHE-9977388) and the UK X-ray facility with funds from the MRI program of the National Science Foundation (grants CHE-0319176 and CHE-1625732). Thanks to the staff of CIC, Boston University for running mass spectrometry samples. We thank Prof. Dong-Sheng Yang and Prof. John P. Selegue for helpful comments on kinetics and chemistry, respectively. G. B. thanks the ULB-VUB computing centre for providing high performance computing facilities and useful technical support.

FundersFunder number
National Science Foundation (NSF)CHE-0319176, CHE-9977388, CHE-1625732

    ASJC Scopus subject areas

    • Inorganic Chemistry

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