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A coordination chemistry dichotomy for icosahedral carborane-based ligands

Nature Chemistry volume 3, pages 590–596 (2011)Cite this article

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Abstract

Although the majority of ligands in modern chemistry take advantage of carbon-based substituent effects to tune the sterics and electronics of coordinating moieties, we describe here how icosahedral carboranes—boron-rich clusters—can influence metal–ligand interactions. Using a series of phosphine–thioether chelating ligands featuring meta- or ortho-carboranes grafted on the sulfur atom, we were able to tune the lability of the platinum–sulfur interaction of platinum(II)–thioether complexes. Experimental observations, supported by computational work, show that icosahedral carboranes can act either as strong electron-withdrawing ligands or electron-donating moieties (similar to aryl- or alkyl-based groups, respectively), depending on which atom of the carborane cage is attached to the thioether moiety. These and similar results with carborane-selenol derivatives suggest that, in contrast to carbon-based ligands, icosahedral carboranes exhibit a significant dichotomy in their coordination chemistry, and can be used as a versatile class of electronically tunable building blocks for various ligand platforms.

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Figure 1: Coordination chemistry and electronic characteristics of phosphine–thioether (P,S) ligands.
Figure 2: Structures of the carborane thiols (I, II, III and V) used to synthesize the (P,S) chelate ligands investigated in this study.
Figure 3: Synthetic scheme outlining the synthesis of Pt(II) complexes.
Figure 4: Characterization of the ligands.
Figure 5: Crystallographically derived X-ray structure representations of closed carborane-based Pt(II) complexes 4a–4d.
Figure 6: Studies of carborane-selenol derivatives.

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Acknowledgements

This research was supported by the National Science Foundation (NSF), the Army Research Office (ARO), the Defense Threat Reduction Agency (DTRA), and the Air Force Office of Scientific Research (AFOSR) (through a Multidisciplinary University Research Initiative (MURI) award). A.M.S. is grateful to the Department of Education for a Graduate Assistance in Areas of National Need (GAANN) Fellowship, and Northwestern University for a Presidential Fellowship. The authors thank the Northwestern University Integrated Molecular Structure Education and Research Center (IMSERC) staff for providing invaluable assistance with analytical instrumentation.

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Authors and Affiliations

  1. Department of Chemistry and the International Institute for Nanotechnology, Northwestern University, 2145 Sheridan Road, Evanston, 60208, lllinois, USA

    Alexander M. Spokoyny, Charles W. Machan, Daniel J. Clingerman, Mari S. Rosen, Michael J. Wiester, Robert D. Kennedy, Charlotte L. Stern, Amy A. Sarjeant & Chad A. Mirkin

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Contributions

A.M.S. originated and developed the concept with C.A.M., who supervised and guided the research. All experiments were designed and performed by A.M.S., C.W.M., D.J.C., M.S.R., M.J.W. and R.D.K. A.M.S. and C.W.M. performed all computational studies. C.L.S., A.A.S. and R.D.K. performed all crystallographic studies. A.M.S. and C.A.M. co-wrote the manuscript. All authors discussed the results and commented on the manuscript during its preparation.

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Correspondence to Chad A. Mirkin.

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Supplementary information

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Supplementary information (PDF 2834 kb)

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Crystallographic data for compound 1a (CIF 38 kb)

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Crystallographic data for compound 1c (CIF 35 kb)

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Crystallographic data for compound 1d (CIF 38 kb)

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Crystallographic data for compound 2a (CIF 37 kb)

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Crystallographic data for compound 2c (CIF 37 kb)

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Crystallographic data for compound 2d (CIF 45 kb)

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Crystallographic data for compound 2f (CIF 20 kb)

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Crystallographic data for compound 2g (CIF 16 kb)

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Crystallographic data for compound 3i-BF4 (CIF 25 kb)

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Crystallographic data for compound 4a (CIF 70 kb)

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Crystallographic data for compound 4b (CIF 139 kb)

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Crystallographic data for compound 4c (CIF 140 kb)

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Crystallographic data for compound 4d (CIF 148 kb)

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Crystallographic data for compound 4e (CIF 29 kb)

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Crystallographic data for compound 4f (CIF 67 kb)

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Crystallographic data for compound 4g (CIF 53 kb)

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Crystallographic data for compound 4h (CIF 49 kb)

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Crystallographic data for compound 4i (CIF 19 kb)

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Spokoyny, A., Machan, C., Clingerman, D. et al. A coordination chemistry dichotomy for icosahedral carborane-based ligands. Nature Chem 3, 590–596 (2011). https://doi.org/10.1038/nchem.1088

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