A Zeolite‐Supported Molecular Ruthenium Complex with η6‐C6H6 Ligands: Chemistry Elucidated by Using Spectroscopy and Density Functional Theory |
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| Authors: | Isao Ogino Mingyang Chen Jason Dyer Philip W Kletnieks James F Haw Prof David A Dixon Prof Bruce C Gates Prof |
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| Institution: | 1. Department of Chemical Engineering and Materials Science, University of California, Davis, Davis, CA, 95616 (USA), Fax: (+1)?530‐752‐1031;2. Department of Chemistry, University of Alabama, Tuscaloosa, AL, 35487 (USA), Fax: (+1)?205‐348‐4704;3. Department of Chemistry, University of Southern California, Los Angeles, CA 90089 (USA) |
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| Abstract: | An essentially molecular ruthenium–benzene complex anchored at the aluminum sites of dealuminated zeolite Y was formed by treating a zeolite‐supported mononuclear ruthenium complex, Ru(acac)(η2‐C2H4)2]+ (acac=acetylacetonate, C5H7O2?), with 13C6H6 at 413 K. IR, 13C NMR, and extended X‐ray absorption fine structure (EXAFS) spectra of the sample reveal the replacement of two ethene ligands and one acac ligand in the original complex with one 13C6H6 ligand and the formation of adsorbed protonated acac (Hacac). The EXAFS results indicate that the supported Ru(η6‐C6H6)]2+ incorporates an oxygen atom of the support to balance the charge, being bonded to the zeolite through three Ru? O bonds. The supported ruthenium–benzene complex is analogous to complexes with polyoxometalate ligands, consistent with the high structural uniformity of the zeolite‐supported species, which led to good agreement between the spectra and calculations at the density functional theory level. The calculations show that the interaction of the zeolite with the Hacac formed on treatment of the original complex with 13C6H6 drives the reaction to form the ruthenium–benzene complex. |
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| Keywords: | density functional calculations EXAFS spectroscopy NMR spectroscopy ruthenium zeolites |
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