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A general method for metallocluster site-differentiation

Nature Synthesis volume 2, pages 740–748 (2023)Cite this article

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Abstract

The deployment of metalloclusters in applications such as catalysis and materials synthesis requires robust methods for site-differentiation: the conversion of clusters with symmetric ligand spheres to those with unsymmetrical ligand spheres. However, imparting precise patterns of site-differentiation is challenging because, compared with mononuclear complexes, the ligands bound to clusters exert limited spatial and electronic influence on one another. Here, we report a method that uses sterically encumbering ligands to bind to only a subset of a cluster’s coordination sites. Specifically, we show that homoleptic, phosphine-ligated Fe–S clusters undergo ligand substitution with N-heterocyclic carbenes to give heteroleptic clusters in which the resultant clusters’ site-differentiation patterns are encoded by the steric profile of the incoming N-heterocyclic carbene. This method affords access to every site-differentiation pattern for cuboidal [Fe4S4] clusters and can be extended to other cluster types, particularly in the stereoselective synthesis of site-differentiated Chevrel-type [Fe6S8] clusters.

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Fig. 1: Challenges in metallocluster site-differentiation illustrated for a tetrahedral cluster.
Fig. 2: Site-differentiation of [Fe4S4]+ clusters using remote steric effects.
Fig. 3: Expanding the scope of site-differentiation to develop a predictable model for determining the maximum number of substitution events, m.
Fig. 4: Stereoselective site-differentiation of [Fe6S8]+ clusters.

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Data availability

All characterization data, computational data and experimental protocols are provided in the Supplementary Information. Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2214357–2214363. Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures. Coordinates of optimized structures are included as Supplementary Information.

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Acknowledgements

The authors thank N. B. Lewis and M. Kumar for their assistance with mass spectrometry experiments and P. Müller for assistance with XRD experiments. This work was supported by the National Institute of General Medical Sciences of the National Institutes of Health under award number R01GM136882 (D.L.M.S.) and by seed funding from the American Chemical Society Petroleum Research Fund under award number 60568-DNI3 (D.L.M.S.). A.C.B. acknowledges fellowships from MathWorks, the National Science Foundation (Graduate Research Fellowship no. 1122374) and the Fannie and John Hertz Foundation.

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Authors and Affiliations

  1. Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, USA

    Trever M. Bostelaar, Alexandra C. Brown, Arun Sridharan & Daniel L. M. Suess

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Contributions

T.M.B., A.C.B. and A.S. performed the experiments. T.M.B., A.C.B., A.S. and D.L.M.S. analysed the data and contributed to the manuscript writing.

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Correspondence to Daniel L. M. Suess.

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Nature Synthesis thanks the anonymous reviewers for their contribution to the peer review of this work. Primary Handling Editor: A. Groves, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Synthetic procedures and supplemental data.

Supplementary Data 1

Crystallographic data for 2; CCDC 2214363.

Supplementary Data 2

Crystallographic data for 3; CCDC 2214362.

Supplementary Data 3

Crystallographic data for 4; CCDC 2214361.

Supplementary Data 4

Crystallographic data for 5; CCDC 2214359.

Supplementary Data 5

Crystallographic data for 7; CCDC 2214360.

Supplementary Data 6

Crystallographic data for 9; CCDC 2214357.

Supplementary Data 7

Crystallographic data for 10; CCDC 2214358.

Supplementary Data 8

Coordinate files of optimized mononuclear complexes.

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Bostelaar, T.M., Brown, A.C., Sridharan, A. et al. A general method for metallocluster site-differentiation. Nat. Synth 2, 740–748 (2023). https://doi.org/10.1038/s44160-023-00286-7

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