NDLI: Structural trends in ten-vertex endohedral clusters, $M@E_{10}$ and the synthesis of a new member of the family, $[Fe@Sn

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Ingram, Matthew D. Zhou, Binbin Duckworth, Jack C. A. Mcgrady, John E. Krämer, Tobias Goicoechea, Jose M.
Description	Author Affiliation: Krämer T ( Department of Chemistry, Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.)
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 $[Ni@In_{10}]^{10−}$ to highly electron rich (>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.
ISSN	14779226
Issue Number	34
Journal	Dalton Trans.
Volume Number	42
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2013-09-14
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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