A Highly Asymmetric Gold(III) η3 -Allyl Complex.

Marte Sofie Martinsen Holmsen,Sigurd Øien‐Ødegaard,Ainara Nova,Mats Tilset,Richard H Heyn

doi:10.1002/anie.201912315

Marte Sofie Martinsen Holmsen, Sigurd Øien‐Ødegaard + Show 3 more

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https://doi.org/10.1002/anie.201912315

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Abstract

A highly asymmetric AuIII η3‐allyl complex has been generated by treating Au(η1‐allyl)Br(tpy) (tpy=2‐(p‐tolyl)pyridine) with AgNTf2. The resulting η3‐allyl complex has been characterized by NMR spectroscopy and X‐ray crystallography. DFT calculations and variable temperature 1H NMR suggest that the allyl ligand is highly fluxional.

Highlights

Complex 2 was obtained in 52–69 % yield and characterized by NMR, MS, elemental analysis and X-ray diffraction analysis.[13] The characteristic resonances of the protons on the allyl ligand are observed in the 1H NMR spectrum of 2; the three vinylic signals are found at d = 6.28 (Hb, see labelling in Scheme 1), 5.48 (Hc), and 5.02 (Hd)
A highly asymmetric AuIII h3-allyl complex has been generated by treating Au(h1-allyl)Br(tpy) (tpy = 2-(p-tolyl)pyridine) with AgNTf2
Despite that the allyl ligand is one of the classical unsaturated, delocalized ligands in organometallic chemistry, AuIII h3-allyl complexes have been rarely described in the literature

Summary

Introduction

Complex 2 was obtained in 52–69 % yield and characterized by NMR, MS, elemental analysis and X-ray diffraction analysis.[13] The characteristic resonances of the protons on the allyl ligand are observed in the 1H NMR spectrum of 2; the three vinylic signals are found at d = 6.28 (Hb, see labelling in Scheme 1), 5.48 (Hc), and 5.02 (Hd). The fact that a coalesced signal is seen for the two Ha, but not for Hc and Hd, suggests that double bond decoordination/recoordination of the h3-allyl ligand occurs selectively trans to the tpy-C atom in 3 a.

Results

Conclusion