Jump to main content
Jump to site search

Issue 35, 2017
Previous Article Next Article

The structural landscape in 14-vertex clusters of silicon, M@Si14: when two bonding paradigms collide

Author affiliations

Abstract

The structural chemistry of the title clusters has been the source of controversy in the computational literature because the identity of the most stable structure appears to be pathologically dependent on the chosen theoretical model. The candidate structures include a D3h-symmetric ‘fullerene-like’ isomer with 3-connected vertices (A), an ‘arachno’ architecture (B) and an octahedral isomer with high vertex connectivities typical of ‘closo’ electron-deficient clusters (C). The key to understanding these apparently very different structures is the fact that they make use of the limited electron density available from the endohedral metal in very different ways. Early in the transition series the favoured structure is the one that maximises transfer of electron density from the electropositive metal to the cage whereas for later metals it is the one that minimises repulsions with the increasingly core-like d electrons. The varying role of the d electrons across the transition series leads directly to strong functional dependency, and hence to the controversy in the literature.

Graphical abstract: The structural landscape in 14-vertex clusters of silicon, M@Si14: when two bonding paradigms collide

Back to tab navigation

Supplementary files

Publication details

The article was received on 22 Jun 2017, accepted on 07 Aug 2017 and first published on 07 Aug 2017


Article type: Paper
DOI: 10.1039/C7DT02257C
Citation: Dalton Trans., 2017,46, 11636-11644
  •   Request permissions

    The structural landscape in 14-vertex clusters of silicon, M@Si14: when two bonding paradigms collide

    X. Jin, V. Arcisauskaite and J. E. McGrady, Dalton Trans., 2017, 46, 11636
    DOI: 10.1039/C7DT02257C

Search articles by author

Spotlight

Advertisements