Our research group is interested in the solution-phase reactivity of “naked” polyanionic clusters of the group 14 and 15 elements.[1c,2c] These species can be used as precursors for a wide range of compounds with interesting structures, many of which disobey established rules for bonding. For example, we have pioneered the study of open-shell main group clusters featuring interstitial transition metal atoms, such as [Fe@Ge10]2− and [Ru@Ge12]3− (Figure 1).[3c,4c] These species represent molecular models of transition-metal/main-group alloys which have found numerous applications in materials science and catalysis.
More recently, we have focused further into the applications of Zintl clusters towards catalysis. For example, the reaction between [Rh(COD)Cl]2 and K[Ge9{Si(SiMe3)3}3] produces a neutral, alkane soluble cluster, [η4-Ge9{Si(SiMe3)3}3]Rh(COD) (Figure 2), which is the first example of a Zintl cluster homogeneous catalyst, catalysing the hydrogenation or cyclic alkenes at room temperature.[5c]
These promising results represent the first steps in a nascent area of chemistry where many interesting breakthroughs await.
[1c] S. C. Sevov, J. M. Goicoechea, Organometallics 2006, 25, 5678.
[2c] R. S. P. Turbervill, J. M. Goicoechea, Chem. Rev. 2014, 114, 10807.
[3c] B. Zhou, M. S. Denning, D. L. Kays, J. M. Goicoechea, J. Am. Chem. Soc. 2009, 131, 2802.
[4c] G. Espinoza-Quintero, J. C. A. Duckworth, W. K. Myers, J. E. McGrady, J. M. Goicoechea, J. Am. Chem. Soc. 2014, 136, 1210.
[5c] O. P. E. Townrow, C. Chung, S. A. Mcgregor, A. S. Weller, J. M. Goicoechea, J. Am. Chem. Soc. 2020, 142, 18330.
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