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

Producción científica: Article › revisión exhaustiva

21 Citas (Scopus)

Resumen

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.

Idioma original	English
Páginas (desde-hasta)	6273-6282
Número de páginas	10
Publicación	Dalton Transactions
Volumen	48
N.º	18
DOI	https://doi.org/10.1039/c8dt05155k
Estado	Published - 2019

Nota bibliográfica

Publisher Copyright:
© The Royal Society of Chemistry 2019.

Financiación

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.

Financiadores	Número del financiador
National Science Foundation Arctic Social Science Program	CHE-0319176, CHE-9977388, CHE-1625732

ASJC Scopus subject areas

Inorganic Chemistry

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10.1039/c8dt05155k

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abstract = "The reactivity of bidentate AuIII-Cl species, [(C\textasciicircum{}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\textasciicircum{}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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AU - Parkin, Sean

AU - Berger, Gilles

AU - Awuah, Samuel G.

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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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