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Alkylruthenium Complexes Containing Polypyridyl Ligands: Synthesis, Characterization, and Immobilization on Silica
Author(s) -
Huang Enrique Kwan,
Cheung WaiMan,
Chan KaWang,
Lam Frank LeungYuk,
Hu Xijun,
Zhang QianFeng,
Williams Ian D.,
Leung WaHung
Publication year - 2013
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201300043
Subject(s) - chemistry , alkylation , tetrahydrofuran , ruthenium , yield (engineering) , medicinal chemistry , benzene , nuclear magnetic resonance spectroscopy , crystal structure , stereochemistry , catalysis , crystallography , organic chemistry , solvent , materials science , metallurgy
The treatment of [Ru(CO) 2 Cl 2 ] x with 4,4′,4″‐tri‐ tert ‐butyl‐2,2′:6′,6″‐terpyridyl (tbtpy) in tetrahydrofuran at reflux afforded trans ‐[Ru(tbtpy)Cl 2 (CO)] ( 1 ). The alkylation of complex 1 with excess Me 3 SiCH 2 MgCl afforded a mixture of trans ‐[Ru(tbtpy)(CH 2 SiMe 3 ) 2 (CO)] ( 2 ) and trans ‐[Ru(tbtpy)(CH 2 SiMe 3 )Cl(CO)] ( 3 ), whereas complex 3 could be obtained in good yield by the alkylation of complex 1 with 1 equiv. of Me 3 SiCH 2 MgCl. On the other hand, the alkylation of 1 with MeLi and PhCH 2 MgBr afforded the monoalkyl complexes [Ru(tbtpy)(Me)Cl(CO)] ( 4 ) and [Ru(tbtpy)(CH 2 Ph)Cl 0.5 Br 0.5 (CO)] ( 5 ), respectively. The crystal structure of complex 5 was determined. Complex 2 and the previously prepared mer ‐[Ru(dtbpy)(CH 2 SiMe 3 ) 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. 1 H NMR spectroscopy indicated that the reaction of complex 2 and [Ru(dtbpy)(CH 2 SiMe 3 ) 3 (NO)] with SBA‐15 in C 6 D 6 resulted in the formation of approximately 1 equiv. of SiMe 4 , which suggests the grafted species are possibly (≡SiO)Ru(tbtpy)(CH 2 SiMe 3 )(CO) and (≡SiO)Ru(dtbpy)(CH 2 SiMe 3 ) 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.