Hetero- and homo-nuclear bimetallic ruthenol complexes by dehydrogenative metallacyclization of Ru(CO)3(bi-1,7-cyclooctadienyl), preparation and x-ray structure of Fe(CO)3(C16H22), RuFe(CO)6(C16H22) and Ru2(CO)6(C16H20) |
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Authors: | Ippei Noda Hajime Yasuda Akira Nakamura |
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Affiliation: | Department of Macromolecular Science, Faculty of Science, Osaka University, Toyonaka, Osaka 560 Japan |
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Abstract: | The reaction of M3(CO)12 (M = Ru, Fe) with excess bi-2,7-cyclooctadienyl (C16H22) 1 gave a mononuclear complex M(CO)3(1,2,1′-2′-η4-C16H22), 2a (M = Ru) or 3a (M = Fe), in good yield. Treatment of 2a with Fe3(CO)12 or reaction of 3a with Ru3(CO)12 gave the heterobimetallic complex RuFe(CO)6(C10H22) consisting of a ruthenacyclopentadiene unit coordinated to an Fe(CO)3 fragment, as confirmed by 1H NMR and X-ray studies. The corresponding homobimetallic complex Ru2(CO)6(C16H22) was obtained from the 1:1 reaction of 2a with Ru3(CO)12, while the direct reaction of 1 with Ru3(CO)12 gave Ru2(CO)6(C16H20) preferentially with a loss of two hydrogen atoms. The pathway for formation of these bimetallic complexes was interpreted as a dehydrogenative metallacyclization followed by hydrogen transfer. |
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