Alkylruthenium Complexes Containing Polypyridyl Ligands: Synthesis, Characterization, and Immobilization on Silica

Autor: Ian D. Williams, Enrique Kwan Huang, Ka Wang Chan, Frank Leung Yuk Lam, Wai-Man Cheung, Qian-Feng Zhang, Xijun Hu, Wa-Hung Leung
Rok vydání: 2013
Předmět:
Zdroj: European Journal of Inorganic Chemistry. 2013:2893-2899
ISSN: 1099-0682
1434-1948
DOI: 10.1002/ejic.201300043
Popis: The treatment of [Ru(CO)2Cl2]x with 4,4′,4″-tri-tert-butyl-2,2′:6′,6″-terpyridyl (tbtpy) in tetrahydrofuran at reflux afforded trans-[Ru(tbtpy)Cl2(CO)] (1). The alkylation of complex 1 with excess Me3SiCH2MgCl afforded a mixture of trans-[Ru(tbtpy)(CH2SiMe3)2(CO)] (2) and trans-[Ru(tbtpy)(CH2SiMe3)Cl(CO)] (3), whereas complex 3 could be obtained in good yield by the alkylation of complex 1 with 1 equiv. of Me3SiCH2MgCl. On the other hand, the alkylation of 1 with MeLi and PhCH2MgBr afforded the monoalkyl complexes [Ru(tbtpy)(Me)Cl(CO)] (4) and [Ru(tbtpy)(CH2Ph)Cl0.5Br0.5(CO)] (5), respectively. The crystal structure of complex 5 was determined. Complex 2 and the previously prepared mer-[Ru(dtbpy)(CH2SiMe3)3(NO)] (dtbpy = 4,4′-di-tert-butyl-2,2′-bipyridyl) were immobilized on SBA-15 by treating the Ru complexes with SBA-15 in benzene at room temperature. 1H NMR spectroscopy indicated that the reaction of complex 2 and [Ru(dtbpy)(CH2SiMe3)3(NO)] with SBA-15 in C6D6 resulted in the formation of approximately 1 equiv. of SiMe4, which suggests the grafted species are possibly (≡SiO)Ru(tbtpy)(CH2SiMe3)(CO) and (≡SiO)Ru(dtbpy)(CH2SiMe3)2(NO), respectively. The Ru-grafted SBA-15 materials were characterized by IR, reflectance UV/Vis, and X-ray photoelectron spectroscopy as well as transmission electronic microscopy, and their catalytic performance in the oxidation of benzyl alcohol with tert-butyl hydroperoxide was examined.
Databáze: OpenAIRE
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