TY - JOUR
T1 - Synthesis of ruthenium–bis(silyl) chelate complexes without carbonyl ligands by reactions of a bis(allyl)ruthenium(II) complex with bis(hydrosilyl)xanthene and phosphines
AU - Kitano, Takeo
AU - Komuro, Takashi
AU - Sato, Keita
AU - Tobita, Hiromi
N1 - Funding Information:
This work was supported by JSPS KAKENHI [grant numbers JP25410058 , JP15H03782 , JP16K05714 , and JP19K05490 ] from the Japan Society for the Promotion of Science (JSPS) . We also acknowledge the Research and Analytical Center for Giant Molecules, Tohoku University, for mass spectroscopic measurements and elemental analysis.
Publisher Copyright:
© 2020 Elsevier B.V.
PY - 2020/7/15
Y1 - 2020/7/15
N2 - Ruthenium complexes bearing a xanthene-based bis(silyl) chelate ligand without CO ligands, Ru(κ3Si,O,Si-xantsil)(H)[PCy2(η3-C6H8)] (1) and Ru(κ2Si,Si-xantsil)(η6-toluene)(L) (L = cyclooctene (coe) (2) and PPh3 (3)), were synthesized by reactions of Ru(η3-2-methylallyl)2(cod) (A, cod = 1,5-cyclooctadiene) with 4,5-bis(dimethylsilyl)-9,9-dimethylxanthene (xantsilH2) in the presence of phosphines PR3 (R = cyclohexyl (Cy), cyclopentyl (Cyp), and Ph) in cyclohexane or toluene at 60 °C. Complexes 1–3 were fully characterized by X-ray crystallography and NMR spectroscopy. In the case of the reaction with PCy3, complex 1 bearing a phosphine–η3-cyclohexenyl chelate ligand was formed via activation of three sp3-C–H bonds on a cyclohexyl group and hydrogenation of 1,5-cyclooctadiene to cyclooctene. Complex 3 was found to undergo exchange of the η6-toluene ligand with benzene at room temperature.
AB - Ruthenium complexes bearing a xanthene-based bis(silyl) chelate ligand without CO ligands, Ru(κ3Si,O,Si-xantsil)(H)[PCy2(η3-C6H8)] (1) and Ru(κ2Si,Si-xantsil)(η6-toluene)(L) (L = cyclooctene (coe) (2) and PPh3 (3)), were synthesized by reactions of Ru(η3-2-methylallyl)2(cod) (A, cod = 1,5-cyclooctadiene) with 4,5-bis(dimethylsilyl)-9,9-dimethylxanthene (xantsilH2) in the presence of phosphines PR3 (R = cyclohexyl (Cy), cyclopentyl (Cyp), and Ph) in cyclohexane or toluene at 60 °C. Complexes 1–3 were fully characterized by X-ray crystallography and NMR spectroscopy. In the case of the reaction with PCy3, complex 1 bearing a phosphine–η3-cyclohexenyl chelate ligand was formed via activation of three sp3-C–H bonds on a cyclohexyl group and hydrogenation of 1,5-cyclooctadiene to cyclooctene. Complex 3 was found to undergo exchange of the η6-toluene ligand with benzene at room temperature.
KW - Chelate ligand
KW - Phosphine
KW - Ruthenium
KW - Silyl complex
KW - Xanthene
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U2 - 10.1016/j.jorganchem.2020.121316
DO - 10.1016/j.jorganchem.2020.121316
M3 - Article
AN - SCOPUS:85084594944
VL - 919
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
M1 - 121316
ER -