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Si@Al 14 (N(Dipp)SiMe 3 ) 6 : A Si‐Centered Metalloid Aluminum Cluster and the Reinvestigation of Si@Al 14 Cp* 6
Author(s) -
Huber Michael,
Hartig Jens,
Koch Katharina,
Schnöckel Hansgeorg
Publication year - 2009
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200801366
Subject(s) - crystallography , cluster (spacecraft) , disproportionation , atom (system on chip) , crystal structure , silicon , chemistry , metastability , materials science , organic chemistry , biochemistry , computer science , embedded system , programming language , catalysis
The preparation and X‐ray structure of Si@Al 14 R 6 (R = Cp*, N(Dipp)SiMe 3 ; Dipp = 2,6 ‐ iPr 2 –C 6 H 3 ) are described via the disproportionation and substitution reaction of a metastable AlCl solution. One silicon atom occupies the center of an Al 8 cube. This central unit is stabilized through capping of six AlR moieties above the faces of the cube. These findings open the door for a reinvestigation of Si@Al 14 Cp* 6 through MALDI, DFT and X‐ray investigations: Caused by the preparation procedure a small part of the Si@Al 14 Cp* 6 clusters are partially oxidized by chlorine and one of the eight aluminum atoms of the cube is substituted by a Si atom: Thus, within the crystal about 1 / 3 of the SiAl 14 Cp* 6 clusters are Si 2 Al 13 Cp* 6 Cl species causing a more unsymmetrical arrangement of all cluster species than those observed in crystalline SiAl 14 (N(Dipp)SiMe 3 ) 6 . The serious problems during the solution of the crystal structure of Si@Al 14 Cp* 6 caused by only slightly modified cluster species may be a strong hint at being careful with the interpretation of any nanoscale species: Even very small modifications (e.g. a single silicon atom i.e. neighbor element of aluminum containing only one more electron and proton substitutes one aluminum atom) cause drastical structural changes and consequently also different e.g. electric properties can be expected.