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

doi:10.1039/c8dt05155k

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 journal › Article › peer-review

17 Scopus citations

Abstract

The reactivity of bidentate Au^III-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 Au^III intermediate. Kinetic studies of the reaction support a second-order rate process.

Original language	English
Pages (from-to)	6273-6282
Number of pages	10
Journal	Dalton Transactions
Volume	48
Issue number	18
DOIs	https://doi.org/10.1039/c8dt05155k
State	Published - 2019

Bibliographical note

Funding Information:
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.

Publisher Copyright:
© The Royal Society of Chemistry 2019.

ASJC Scopus subject areas

Inorganic Chemistry

Access to Document

10.1039/c8dt05155k

Cite this

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title = "Direct intramolecular carbon(sp2)-nitrogen(sp2) reductive elimination from gold(iii)",

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.",

author = "Kim, {Jong Hyun} and Mertens, {R. Tyler} and Amal Agarwal and Sean Parkin and Gilles Berger and Awuah, {Samuel G.}",

note = "Funding Information: 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. Publisher Copyright: {\textcopyright} The Royal Society of Chemistry 2019.",

year = "2019",

doi = "10.1039/c8dt05155k",

language = "English",

volume = "48",

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T1 - Direct intramolecular carbon(sp2)-nitrogen(sp2) reductive elimination from gold(iii)

AU - Kim, Jong Hyun

AU - Mertens, R. Tyler

AU - Agarwal, Amal

AU - Parkin, Sean

AU - Berger, Gilles

AU - Awuah, Samuel G.

N1 - Funding Information: 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. Publisher Copyright: © The Royal Society of Chemistry 2019.

PY - 2019

Y1 - 2019

N2 - 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.

AB - 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.

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