Higher-Coordinated Molecular Silicon Compounds

  • Jörg Wagler
  • Uwe Böhme
  • Edwin KrokeEmail author
Part of the Structure and Bonding book series (STRUCTURE, volume 155)


In silicon compounds the Si atoms are known to be fourfold coordinated in most cases. However, there are several cationic, anionic, and neutral molecular species containing hypercoordinated – i.e., five- and sixfold coordinated (and in few cases even higher coordinated) – silicon atoms. This class of compounds ranges from long known stable inorganic species such as SiF6 2− to many different organometallic compounds with multidentate chelate ligands. Although this field has been known since the early nineteenth century and expanded significantly in the twentieth century, very interesting advances have been developed in the past decade. These include the extension of established synthesis routes to novel ligand systems via substitution, addition, and oxidative addition, among others. A number of new organic ligand systems have been successfully applied leading to unprecedented coordination modes of the silicon atoms. The structures of the obtained compounds have been analyzed thoroughly in many cases providing detailed insights into structure and bonding situations in hypercoordinated silicon complexes. Besides the classical silicon compounds with donor atoms such as H, C, Cl, F, O, and N, many novel examples with main group metal as well as transition metal atoms in the coordination sphere of silicon have been reported.


Chelate ligand Donor atom Hypercoordination Silicon complex Structure Synthesis 



Atoms in molecules (see also QTAIM)














Coordination number






Cambridge Structural Database












Dimethyl sulfoxide










Mesityl, 2,4,6-trimethylphenyl (not methanesulfonyl)


Methimazolyl (1-methyl-2-mercaptoimidazolyl)


Natural bond order


N-heterocyclic carbene


N-heterocyclic silylene


















Quantum theory of atoms in molecules


Square pyramid (or square pyramidal)


Trigonal bipyramid (or trigonal-bipyramidal)


Trifluoromethanesulfonyl (triflyl)






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Copyright information

© Springer-Verlag Berlin Heidelberg 2013

Authors and Affiliations

  1. 1.TU Bergakademie FreibergInstitut fürAnorganische ChemieFreibergGermany

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