The Clusters Subgroup

The research in our team is focused on the coordination chemistry of low valent group 12/13 organyls ECp* (E = Al, Ga, Zn) to transition metals (TM). After years of hunting for crystal structures of bimetallic complexes, we became more insterested in analyzing reaction solutions containing inseparable mixtures of reactive species of intermetallic clusters of the type [TMxEyLz] (L = ligand) from which nothing is crystallizing nicely. Sheding light into such “living cluster libraries” is possible by mass spectrometric analysis (ESI and LIFDI). Currently, we are studying three main research sectors:

1) the fundamental understanding of intermetallic cluster mixtures by MS analysis: how can peaks in the MS spectra unambiguously identified? What sort of fragmentation behavior is observed? How can mass spectrometry help to deduce fundamental mechanisms of cluster growth and reactivity?

2) surface activation of the cluster mixtures - how can open coordination sites be created? What sort of stabilizing ligands L and synthetic protocols are suited for generation of “naked” metal sites at the clusters´ surface, possibly prone to enhanced reactivity?

3) the interaction of the cluster libraries with small molecules and organic functionalities: Does the reaction behavior allow to draw any parallels to solid state catalysts?

Exploring Cu/Al cluster growth and reactivity: From embryonic building blocks to intermetalloid, open-shell superatoms

M. Schütz, C. Gemel, M. Muhr, C. Jandl, S. Kahlal, J.-Y. Saillard, R. A. Fischer

Chem. Sci. 202112, 6588


All-zinc coordinated nickel-complexes as molecular mimics for NiZn catalyst surfaces, a density functional theory study

J. Hornung, M. Muhr, C. Gemel, R. A. Fischer

Dalton Trans. 201948(31), 11743–11748.


Embryonic brass: pseudo two electron Cu/Zn clusters

H. Banh, J. Hornung, T. Kratz, C. Gemel, A. Pöthig, F. Gam, S. Kahlal, J.-Y. Saillard, R. A. Fischer

Chem. Sci. 2018, 9(48), 8906–8913.


The Mackay-Type Cluster [Cu43Al12](Cp*)12: Open-Shell 67-Electron Superatom with Emerging Metal-Like Electronic Structure

J. Weßing, C. Ganesamoorthy, S. Kahlal, R. Marchal, C. Gemel, O. Cador, A. C. H. Da Silva, J. L. F. Da Silva, J.-I. Saillard, R. A. Fischer

Angew. Chem. Int. Ed. 201857(44), 14630–14634.

DFG Reinhart Koselleck Project Living Libraries of Intermetallic Superatoms

Juarez L. F. da Silva, University of São Paulo, Brazil

Jean-Yves Saillard, Université de Rennes 1, France

Balaji R. Jagirdar, Indian Institute of Science, Bangalore, India