Structural trends in ten-vertex endohedral clusters, M@E10 and the synthesis of a new member of the family, [Fe@Sn-10]3-

Tobias Kraemer, Jack C. A. Duckworth, Matthew D. Ingram, Binbin Zhou, John E. McGrady, Jose M. Goicoechea

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Abstract

The synthesis of a new endohedral ten-vertex Zintl ion cluster, [Fe@Sn-10](3-), isoelectronic with [Fe@Ge-10](3-), is reported. In an attempt to place this new cluster within the context of the known structural chemistry of the M@E-10 family (M = transition metal, E = main group element), we have carried out a detailed electronic structure analysis of the different structural types: viz bicapped square antiprismatic ([Ni@Pb-10](2-), [Zn@In-10](8-)), tetra-capped trigonal prismatic ([Ni@In-10](10-)) and the remarkable pentagonal prismatic [Fe@Ge-10](3-) and [Co@Ge-10](3-). We establish that the structural trends can be interpreted in terms of a continuum of effective electron counts at the E-10 cage, ranging from electron deficient (4n + 2) in [Fe@Ge-10](3-). The effective electron count differs from the total valence electron count in that it factors in the increasingly active role of the metal d electrons towards the left of the transition series. The preference for a pentagonal prismatic geometry in [Fe@Ge-10](3-) emerges as a natural consequence of backbonding to the cage from four orthogonal 3d orbitals of the low-valent metal ion. Our calculations suggest that the new [Fe@Sn-10](3-) cluster should also exhibit structural consequences of backbonding from the metal to the cage, albeit to a less extreme degree than in its Ge analogue. The global minimum lies on a very flat surface connecting D-4d, C-2v and C-3v-symmetric minima, suggesting a very plastic structure that may be easily deformed by the surrounding crystal environment. If so, then this provides a new and quite distinct structural type for the M@E-10 family.

Original languageEnglish
Pages (from-to)12120-12129
Number of pages10
JournalDalton Transactions
Volume42
Issue number34
DOIs
Publication statusPublished - 14 Sep 2013

Keywords

  • DELTAHEDRAL ZINTL IONS
  • GERMANIUM CLUSTERS
  • MAGNETIC-PROPERTIES
  • ELEMENTS
  • ENERGY
  • ANIONS
  • APPROXIMATION
  • ATOMS
  • NI
  • DERIVATIVES

Cite this

Kraemer, T., Duckworth, J. C. A., Ingram, M. D., Zhou, B., McGrady, J. E., & Goicoechea, J. M. (2013). Structural trends in ten-vertex endohedral clusters, M@E10 and the synthesis of a new member of the family, [Fe@Sn-10]3-. Dalton Transactions, 42(34), 12120-12129. https://doi.org/10.1039/c3dt50643f