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. 2024 Feb 26;63(8):3749-3756.
doi: 10.1021/acs.inorgchem.3c03790. Epub 2024 Feb 9.

All-Hydrocarbon-Ligated Superatomic Gold/Aluminum Clusters

Ivan Antsiburov  1 , Max Schütz  1 , Raphael Bühler  1 , Maximilian Muhr  1 , Johannes Stephan  1 , Christian Gemel  1 , Wilhelm Klein  1 , Samia Kahlal  2 , Jean-Yves Saillard  2 , Roland A Fischer  1
Affiliations

All-Hydrocarbon-Ligated Superatomic Gold/Aluminum Clusters

Ivan Antsiburov et al. Inorg Chem. .

Abstract

Key strategies in cluster synthesis include the use of modulating agents (e.g., coordinating additives). We studied the influence of various phosphines exhibiting different steric and electronic properties on the reduction of the Au(I) precursor to Au(0) clusters. We report a synthesis of the bimetallic clusters [Au6(AlCp*)6] = [Au6Al6](Cp*)6 (1) and [HAu7(AlCp*)6] = [HAu7Al6](Cp*)6 (2) (Cp* = pentamethylcyclopentadiene) using Au(I) precursors and AlCp*. The cluster [Au2(AlCp*)5] = [Au2Al5](Cp*)5 (3) was isolated and identified as an intermediate species in the reactions to 1 and 2. The processes of cluster growth and degradation were investigated by in situ 1H NMR and LIFDI-MS techniques. The structures of 1 and 2 were established by DFT geometry optimization. These octahedral clusters can both be described as closed-shell 18-electron superatoms.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Synthesis of the [Au6Al6](Cp*)6 (1)
Scheme 2
Scheme 2. Synthesis of the [HAu7Al6](Cp*)6 (2)
Figure 1
Figure 1
DFT-optimized geometries of the lowest energy isomers [Au6Al6](Cp*)6 (1) and [HAu7Al6](Cp*)6 (2). Color code: Au, yellow; Al, magenta; and C, gray. Hydride ligand of the AuH moiety is shown in red.
Scheme 3
Scheme 3. Synthesis of the [Au2Al5](Cp*)5 (3)
Figure 2
Figure 2
Molecular structure of [Au2Al5](Cp*)5. Au: yellow, Al: pink, and C: gray. H atoms and cocrystallized solvent molecules are omitted, and Cp* ligands drawn in wireframe representation for clarity. Thermal ellipsoids are shown at the 50% probability level.
See this image and copyright information in PMC

References

    1. Bellon P. L.; Cariati F.; Manassero M.; Naldini L.; Sansoni M. Novel gold clusters. Preparation, properties, and X-ray structure determination of salts of octakis(triarylphosphine)enneagold, [Au9L8]X3. J. Chem. Soc. D 1971, (22), 1423–1424. 10.1039/c29710001423. - DOI
    1. Schmid G.; Pfeil R.; Boese R.; Bandermann F.; Meyer S.; Calis G. H. M.; van der Velden J. W. A. Au55[P(C6H5)3]12CI6—ein Goldcluster ungewöhnlicher Größe. Chem. Ber. 1981, 114 (11), 3634–3642. 10.1002/cber.19811141116. - DOI
    1. Briant C. E.; Theobald B. R. C.; White J. W.; Bell L. K.; Mingos D. M. P.; Welch A. J. Synthesis and X-ray structural characterization of the centred icosahedral gold cluster compound [Aul3(PMe2Ph)10Cl2](PF6)3; the realization of a theoretical prediction. J. Chem. Soc., Chem. Commun. 1981, (5), 201–202. 10.1039/c39810000201. - DOI
    1. Mingos D. M. P. Structural and bonding patterns in gold clusters. Dalton Trans. 2015, 44 (15), 6680–6695. 10.1039/C5DT00253B. - DOI - PubMed
    1. Vollenbroek F. A.; Bosman W. P.; Bour J. J.; Noordik J. H.; Beurskens P. T. Reactions of gold-phosphine cluster compounds. Preparation and X-ray structure determination of octakis(triphenylphosphine)octa-gold bis(hexafluorophosphate). J. Chem. Soc., Chem. Commun. 1979, (9), 387–388. 10.1039/C39790000387. - DOI