Reactivity of ruthenium vinylidene complexes containing indenyl/dppe ligands and unsaturated bonds at Cδ with trimethylsilyl azide

Molecules. 2012 Jul 17;17(7):8533-53. doi: 10.3390/molecules17078533.

Abstract

This study presents a new reaction of cationic vinylidene complexes with Me₃SiN₃ (TMSN₃), which yields N-coordinated nitrile complexes 3. Treatment of a ruthenium acetylide precursor containing indenyl and dppe ligands with a series of organic halides produced the corresponding vinylidene complexes 2 in good yield. Further reaction of 2 with TMSN₃ at room temperature produced N-coordinated ruthenium nitrile complexes 3. Unlike the reaction of cyclopropenylruthenium complexes with TMSN₃, which yielded different products depending on the substituent at Cγ, the vinylidene complexes containing unsaturated bonds at Cd yielded similar N-coordinated nitrile complexes. This transformation did not seemingly occur in the reaction of ruthenium vinylidene complexes containing Cp and PPh₃ ligands with TMSN₃. Deprotonation of these vinylidene complexes yielded cyclopropenyl or thermodynamic furylruthenium complexes, depending on the substitute at Cγ. Subsequent reactions of the cyclopropenyl or furylruthenium complexes with TMSN₃ afforded different products.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Azides / chemistry*
  • Coordination Complexes / chemistry*
  • Crystallography, X-Ray
  • Cyclopropanes / chemistry
  • Indenes / chemistry*
  • Ligands
  • Molecular Structure
  • Phosphatidylethanolamines / chemistry
  • Ruthenium / chemistry*
  • Silanes / chemistry*
  • Vinyl Compounds / chemistry*

Substances

  • Azides
  • Coordination Complexes
  • Cyclopropanes
  • Indenes
  • Ligands
  • Phosphatidylethanolamines
  • Silanes
  • Vinyl Compounds
  • azidotrimethylsilane
  • vinylindene
  • 1,2-dipalmitoyl-3-phosphatidylethanolamine
  • cyclopropene
  • Ruthenium