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

Takeo Kitano; Takashi Komuro; Keita Sato; Hiromi Tobita

doi:10.1016/j.jorganchem.2020.121316

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

Takeo Kitano, Takashi Komuro, Keita Sato, Hiromi Tobita

SCI - Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

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.

Original language	English
Article number	121316
Journal	Journal of Organometallic Chemistry
Volume	919
DOIs	https://doi.org/10.1016/j.jorganchem.2020.121316
Publication status	Published - 2020 Jul 15

Keywords

Chelate ligand
Phosphine
Ruthenium
Silyl complex
Xanthene

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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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. / Kitano, Takeo; Komuro, Takashi; Sato, Keita; Tobita, Hiromi.

In: Journal of Organometallic Chemistry, Vol. 919, 121316, 15.07.2020.

Research output: Contribution to journal › Article › peer-review

@article{b05bd891718045ac9dff02ce5b352d9c,

title = "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",

abstract = "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.",

keywords = "Chelate ligand, Phosphine, Ruthenium, Silyl complex, Xanthene",

author = "Takeo Kitano and Takashi Komuro and Keita Sato and Hiromi Tobita",

note = "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. ",

year = "2020",

month = jul,

day = "15",

doi = "10.1016/j.jorganchem.2020.121316",

language = "English",

volume = "919",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

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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.

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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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

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