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Carbon–phosphorus coupling from C^N cyclometalated AuIII complexes

Carbon–phosphorus coupling from C^N cyclometalated AuIII complexes
Carbon–phosphorus coupling from C^N cyclometalated AuIII complexes

With the aim of exploiting new organometallic species for cross-coupling reactions, we report here on the AuIII-mediated Caryl−P bond formation occurring upon reaction of C^N cyclometalated AuIII complexes with phosphines. The [Au(C^N)Cl2] complex 1 featuring the bidentate 2-benzoylpyridine (CCON) scaffold was found to react with PTA (1,3,5-triaza-7-phosphaadamantane) under mild conditions, including in water, to afford the corresponding phosphonium 5 through C−P reductive elimination. A mechanism is proposed for the title reaction based on in situ 31P{1H} NMR and HR-ESI-MS analyses combined with DFT calculations. The C−P coupling has been generalized to other C^N cyclometalated AuIII complexes and other tertiary phosphines. Overall, this work provides new insights into the reactivity of cyclometalated AuIII compounds and establishes initial structure–activity relationships to develop AuIII-mediated C−P cross-coupling reactions.

carbon–phosphorous bond, cross-coupling, density functional calculations, gold(III) cyclometalated compounds, reductive elimination
0947-6539
4226-4231
Bonsignore, Riccardo
bfce63f3-2ab6-4a51-bc21-1ce8202386e1
Thomas, Sophie R.
4cd233f6-5023-4bf9-a5b7-922c72a08a7c
Klooster, Wim T.
64dc0111-f415-4226-9189-45764c0933d9
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Jenkins, Robert L.
7c9a06ba-1439-40e2-a412-7f22697d8280
Bourissou, Didier
74a257f0-27fa-4901-84bf-954f7bcd67d6
Barone, Giampaolo
4f068e39-e3d0-4dbe-aeb4-0a1a08d1d332
Casini, Angela
27012a50-6e79-4b89-b843-c813b358f332
Bonsignore, Riccardo
bfce63f3-2ab6-4a51-bc21-1ce8202386e1
Thomas, Sophie R.
4cd233f6-5023-4bf9-a5b7-922c72a08a7c
Klooster, Wim T.
64dc0111-f415-4226-9189-45764c0933d9
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Jenkins, Robert L.
7c9a06ba-1439-40e2-a412-7f22697d8280
Bourissou, Didier
74a257f0-27fa-4901-84bf-954f7bcd67d6
Barone, Giampaolo
4f068e39-e3d0-4dbe-aeb4-0a1a08d1d332
Casini, Angela
27012a50-6e79-4b89-b843-c813b358f332

Bonsignore, Riccardo, Thomas, Sophie R., Klooster, Wim T., Coles, Simon J., Jenkins, Robert L., Bourissou, Didier, Barone, Giampaolo and Casini, Angela (2020) Carbon–phosphorus coupling from C^N cyclometalated AuIII complexes. Chemistry - A European Journal, 26 (19), 4226-4231. (doi:10.1002/chem.201905392).

Record type: Article

Abstract

With the aim of exploiting new organometallic species for cross-coupling reactions, we report here on the AuIII-mediated Caryl−P bond formation occurring upon reaction of C^N cyclometalated AuIII complexes with phosphines. The [Au(C^N)Cl2] complex 1 featuring the bidentate 2-benzoylpyridine (CCON) scaffold was found to react with PTA (1,3,5-triaza-7-phosphaadamantane) under mild conditions, including in water, to afford the corresponding phosphonium 5 through C−P reductive elimination. A mechanism is proposed for the title reaction based on in situ 31P{1H} NMR and HR-ESI-MS analyses combined with DFT calculations. The C−P coupling has been generalized to other C^N cyclometalated AuIII complexes and other tertiary phosphines. Overall, this work provides new insights into the reactivity of cyclometalated AuIII compounds and establishes initial structure–activity relationships to develop AuIII-mediated C−P cross-coupling reactions.

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Accepted/In Press date: 29 January 2020
e-pub ahead of print date: 29 January 2020
Published date: 1 April 2020
Keywords: carbon–phosphorous bond, cross-coupling, density functional calculations, gold(III) cyclometalated compounds, reductive elimination

Identifiers

Local EPrints ID: 439694
URI: http://eprints.soton.ac.uk/id/eprint/439694
ISSN: 0947-6539
PURE UUID: 42406732-169f-4ef7-a9f0-87f1f779c121
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 29 Apr 2020 16:35
Last modified: 30 Apr 2020 00:27

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Contributors

Author: Riccardo Bonsignore
Author: Sophie R. Thomas
Author: Wim T. Klooster
Author: Simon J. Coles ORCID iD
Author: Robert L. Jenkins
Author: Didier Bourissou
Author: Giampaolo Barone
Author: Angela Casini

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