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Lithiated Clusters from Primary Silylphosphanes and Silylarsanes: Spherical Bodies with and without Li 2 O Filling
Author(s) -
Driess Matthias,
Hoffmanns Ulrich,
Martin Stefan,
Merz Klaus,
Pritzkow Hans
Publication year - 1999
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/(sici)1521-3773(19990917)38:18<2733::aid-anie2733>3.0.co;2-s
Subject(s) - cluster (spacecraft) , polyhedron , crystallography , chemistry , metalation , molar ratio , shell (structure) , primary (astronomy) , stereochemistry , physics , materials science , geometry , organic chemistry , mathematics , catalysis , computer science , programming language , astronomy , composite material
Abstract Molecular clusters with archimedean and platonic shape , which in order to build a closed polyhedron, spontaneously eliminate H 2 or voluntarily encapsulate Li 2 O as a “cluster nucleus”, result from the dilithiation of primary silylphosphanes and silylarsanes with BuLi. Thus, the first mixed‐valent, decameric P 10 Li 16 cluster 1 was obtained from i Pr 3 SiPH 2 and t BuLi (molar ratio 1:2) with strict exclusion of LiOH and Li 2 O, whereas partial metalation in the presence of LiOH initially leads to a dodecameric, Li 2 O‐containing cluster 2 , from which the three‐shell cluster 3 with a [Li 6 O] 4+ core is obtained.