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Structure and reactivity of a mononuclear gold(II) complex

Nature Chemistry volume 9, pages 1249–1255 (2017)Cite this article

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Abstract

Mononuclear gold(II) complexes are very rare labile species. Transient gold(II) species have been suggested in homogeneous catalysis and in medical applications, but their geometric and electronic structures have remained essentially unexplored: even fundamental data, such as the ionic radius of gold(II), are unknown. Now, an unprecedentedly stable neutral gold(II) complex of a porphyrin derivative has been isolated, and its structural and spectroscopic features determined. The gold atom adopts a 2+2 coordination mode in between those of gold(III) (four-coordinate square planar) and gold(I) (two-coordinate linear), owing to a second-order Jahn–Teller distortion enabled by the relativistically lowered 6s orbital of gold. The reactivity of this gold(II) complex towards dioxygen, nitrosobenzene and acids is discussed. This study provides insight on the ionic radius of gold(II), and allows it to be placed within the homologous series of nd9 Cu/Ag/Au divalent ions and the 5d8/9/10 Pt/Au/Hg ‘relativistic’ triad in the periodic table.

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Figure 1
Figure 2: Electronic structure of Au(TPP).
Figure 3: Absorption spectrum of sublimed Au(TPP) in CH2Cl2 at 295 K.
Figure 4: Experimental normalized XANES spectra of [Au(TPP)][PF6] (black), Au(TPP) (red) and Au2Cl2(xantphos) (green).
Figure 5: Molecular structure of the neutral Au(II) complex Au(TPP).
Figure 6: Studies of the reactivity of Au(TPP).

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Acknowledgements

Parts of this research were conducted using the supercomputer Mogon and advisory services offered by Johannes Gutenberg University Mainz (www.hpc.uni-mainz.de), which is a member of the AHRP and the Gauss Alliance. We thank P. Auerbach and M. Mondeshki for collecting the LIFDI mass spectra and assistance with the paramagnetic NMR spectra and R. Jung-Pothmann for collection of the diffraction data. This work was financially supported by the Deutsche Forschungsgemeinschaft (GSC 266, Materials Science in Mainz, scholarship for S.O.). PETRA III is acknowledged for the provision of beamtime at beamline P64. This article is dedicated to G. Huttner on the occasion of his 80th birthday.

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Authors and Affiliations

  1. Institute of Inorganic Chemistry and Analytical Chemistry, Johannes Gutenberg-University, Duesbergweg 10–14, Mainz, D-55128, Germany

    Sebastian Preiß, Christoph Förster, Sven Otto, Luca Carella & Katja Heinze

  2. Graduate School Materials Science in Mainz, Staudingerweg 9, Mainz, D-55128, Germany

    Sven Otto

  3. Department Chemie, University of Paderborn, Warburger Straße 100, Paderborn, D-33098, Germany

    Matthias Bauer & Patrick Müller

  4. Institute of Chemistry, Martin-Luther-Universität Halle-Wittenberg, von-Danckelmann-Platz 4, Halle (Saale), D-06120, Germany

    Dariush Hinderberger & Haleh Hashemi Haeri

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Contributions

S.P. synthesized [Au(TPP)][PF6] and Au(TPP), measured the X-band EPR, NMR, infrared, UV–Vis and mass spectra and studied the reactivity, S.O. made the quantum chemical calculations, C.F. performed the single-crystal XRD analysis, D.H. and H.H.H. measured and interpreted the Q-band EPR spectra, P.M. and M.B. measured and interpreted the X-ray absorption spectra and L.C. measured the magnetic susceptibility data. K.H. conceived and designed the experiments and wrote the paper. All of the authors discussed the results and commented on the manuscript.

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Correspondence to Katja Heinze.

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Supplementary information

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Crystallographic data for compound Au(TPP) (CIF 294 kb)

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Structure factors file for compound Au(TPP) (FCF 210 kb)

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Preiß, S., Förster, C., Otto, S. et al. Structure and reactivity of a mononuclear gold(II) complex. Nature Chem 9, 1249–1255 (2017). https://doi.org/10.1038/nchem.2836

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