Reactions of a Silylyne Complex with Aldehydes: Formation of W?Si?O?C Four-Membered Metallacycles and Their Metathesis-Like Fragmentation |
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| Authors: | Takashi Yoshimoto Prof?Dr Hisako Hashimoto Dr Nozomi Takagi Prof?Dr Shigeyoshi Sakaki Naoki Hayakawa Dr Tsukasa Matsuo Prof?Dr Hiromi Tobita |
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| Institution: | 1. Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai, 980-8578 Japan;2. Elements Strategy Initiative for Catalysts and Batteries, Kyoto University, Nishikyo-ku, Kyoto, 615-8245 Japan;3. Department of Applied Chemistry, Faculty of Science and Engineering, Kindai University, 3-4-1 Kowakae, Higashi-Osaka, 577-8502 Japan |
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| Abstract: | A tungsten silylyne complex having a W≡Si triple bond reacted with two molecules of aldehydes at room temperature to give W?Si?O?C four-membered metallacycles by 2+2] cycloaddition and subsequent formyl hydrogen transfer from one aldehyde molecule to another. Upon heating to 70 °C, the four-membered metallacycles underwent metathesis-like fragmentation cleanly to afford carbyne complexes and “silanoic esters,” in a manner similar to that of metallacyclobutadiene, an intermediate of alkyne metathesis reactions, and dimerization of the latter products gave 1,3-cyclodisiloxanes. The “silanoic ester” was also trapped by pivalaldehyde to give a 2+2] cycloaddition product in high yield. |
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| Keywords: | [2+2] cycloaddition aldehyde metathesis-like fragmentation silylyne complex tungsten |
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