Krämer, Tobias and Duckworth, Jack C A and Ingram, Matthew D and Zhou, Binbin and McGrady, John E. and Goicoechea, Jose M. (2013) Structural trends in ten-vertex endohedral clusters, M@E10 and the synthesis of a new member of the family, [Fe@Sn10]3−. Dalton Transactions, 42. pp. 12120-12129. ISSN 1477-9226

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Abstract

The synthesis of a new endohedral ten-vertex Zintl ion cluster, [Fe@Sn10]3−, isoelectronic with [Fe@Ge10]3−, is reported. In an attempt to place this new cluster within the context of the known structural chemistry of the M@E10 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@Pb10]2−, [Zn@In10]8−), tetra-capped trigonal prismatic ([Ni@In10]10−) and the remarkable pentagonal prismatic [Fe@Ge10]3− and [Co@Ge10]3−. We establish that the structural trends can be interpreted in terms of a continuum of effective electron counts at the E10 cage, ranging from electron deficient (<4n + 2) in [Ni@In10]10− to highly electron rich (>4n + 2) in [Fe@Ge10]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@Ge10]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@Sn10]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 D4d, C2v and C3v-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@E10 family.

Item Type:	Article
Keywords:	Structural trends; ten-vertex endohedral clusters; M@E10; synthesis; new member; family; [Fe@Sn10]3−;
Academic Unit:	Faculty of Science and Engineering > Chemistry Faculty of Science and Engineering > Research Institutes > Hamilton Institute
Item ID:	15505
Identification Number:	https://doi.org/10.1039/c3dt50643f
Depositing User:	Tobias Kraemer
Date Deposited:	15 Feb 2022 14:54
Journal or Publication Title:	Dalton Transactions
Publisher:	Royal Society of Chemistry
Refereed:	Yes
URI:	Publisher
Use Licence:	This item is available under a Creative Commons Attribution Non Commercial Share Alike Licence (CC BY-NC-SA). Details of this licence are available here

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