Reactivity of ruthenium vinylidene complexes containing indenyl/dppe ligands and unsaturated bonds at Cδ with trimethylsilyl azide.
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.
Department of Mathematics and Science (Pre-college), National Taiwan Normal University, New Taipei City 244, Taiwan. hlsung@ntnu.edu.tw
Hui-Ling
HL
Sung
Tze-Min
TM
Her
Wen-Hsien
WH
Su
Chin-Pao
CP
Cheng
D001386:Azides / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003521:Cyclopropanes / Q000737:chemistry; D007192:Indenes / Q000737:chemistry*; D008024:Ligands; D015394:Molecular Structure; D010714:Phosphatidylethanolamines / Q000737:chemistry; D012428:Ruthenium / Q000737:chemistry*; D012821:Silanes / Q000737:chemistry*; D014753:Vinyl Compounds / Q000737:chemistry*
D001386:Azides; D056831:Coordination Complexes; D003521:Cyclopropanes; D007192:Indenes; D008024:Ligands; D010714:Phosphatidylethanolamines; D012821:Silanes; D014753:Vinyl Compounds; C438544:azidotrimethylsilane; C545570:vinylindene; C007510:1,2-dipalmitoyl-3-phosphatidylethanolamine; C021985:cyclopropene; D012428:Ruthenium