Facile access to silicon-functionalized bis-silylene titanium(II) complexes

Burgert Blom, Matthias Driess, Daniel Gallego, Shigeyoshi Inoue

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44 Scopus citations


A series of unprecedented bis-silylene titanium(II) complexes of the type [(η 5-C 5H 5) 2Ti(LSiX) 2] (L=PhC(NtBu) 2; X=Cl, CH 3, H) has been prepared using a phosphane elimination strategy. Treatment of the [(η 5-C 5H 5) 2Ti(PMe 3) 2] precursor (1) with two molar equivalents of the N-heterocyclic chlorosilylene LSiCl (2), results in [(η 5-C 5H 5) 2Ti(LSiCl) 2] (3) with concomitant PMe 3 elimination. The presence of a Si-Cl bond in 3 enabled further functionalization at the silicon(II) center. Accordingly, a salt metathesis reaction of 3 with two equivalents of MeLi results in [(η 5-C 5H 5) 2Ti(LSiMe) 2] (4). Similarly, the reaction of 3 with two equivalents of LiBHEt 3 results in [(η 5-C 5H 5) 2Ti(LSiH) 2] (5), which represents the first example of a bis-(hydridosilylene) metal complex. All complexes were fully characterized and the structures of 3 and 4 elucidated by single-crystal X-ray diffraction analysis. DFT calculations of complexes 3-5 were also carried out to assess the nature of the titanium-silicon bonds. Two σ and one π-type molecular orbital, delocalized over the Si-Ti-Si framework, are observed.

Original languageEnglish
Pages (from-to)13355-13360
Number of pages6
JournalChemistry - A European Journal
Issue number42
StatePublished - 15 Oct 2012
Externally publishedYes


  • N-heterocyclic silylenes
  • density functional calculations
  • donor-acceptor stabilization
  • silicon
  • titanium


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