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Versatility and adaptative behaviour of the P^N chelating ligand MeDalphos within gold(i) π complexes

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Abstract

The hemilabile P^N ligand MeDalphos enables access to a wide range of stable gold(I) π-complexes with unbiased alkenes and alkynes, as well as electron-rich alkenes and for the first time electron-poor ones. All complexes have been characterized by multi-nuclear NMR spectroscopy and whenever possible, by X-ray diffraction analyses. They all adopt a rare tricoordinate environment around gold(I), with chelation of the P^N ligand and side-on coordination of the alkene, including the electron-rich one, 3,4-dihydro-2H-pyrane. The strength of the N → Au coordination varies significantly in the series. It is the way the P^N ligand accommodates the electronic demand at gold, depending on the alkene. Comparatively, when the chelating P^P ligand (ortho-carboranyl)(PPh2)2 is used, gold(I) π-complexes are only isolable with unbiased alkenes. The bonding situation within the gold(I) P^N π-complexes has been thoroughly analyzed by DFT calculations supplemented by Charge Decomposition Analyses (CDA), Natural Bond Orbital (NBO) and Atoms-in-Molecules (AIM) analyses. Noticeable variations in the donation/back-donation ratio, C[double bond, length as m-dash]C weakening, alkene to gold charge transfer and magnitude of the N → Au coordination were observed. Detailed examination of the descriptors for the Au/alkene interaction and the N → Au coordination actually revealed intimate correlation between the two, with linear response of the MeDalphos ligand to the alkene electronics. The P^N ligand displays non-innocent and adaptative character. The isolated P^N gold(I) π-complexes are reactive and catalytically relevant, as substantiated by the chemo and regio-selective alkylation of indoles.

Graphical abstract: Versatility and adaptative behaviour of the P^N chelating ligand MeDalphos within gold(i) π complexes

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Article information


Submitted
17 Dec 2019
Accepted
31 Jan 2020
First published
04 Feb 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020, Advance Article
Article type
Edge Article

Versatility and adaptative behaviour of the P^N chelating ligand MeDalphos within gold(I) π complexes

M. Navarro, A. Toledo, S. Mallet-Ladeira, E. D. Sosa Carrizo, K. Miqueu and D. Bourissou, Chem. Sci., 2020, Advance Article , DOI: 10.1039/C9SC06398F

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