Mechanistic study on dimerization of acetylene with a Nieuwland catalyst |
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Authors: | Takashi Tachiyama Makoto Yoshida Tatsuhiro Aoyagi Shunichi Fukuzumi |
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Institution: | 1. Denki‐Kagaku Kogyo Co. Ltd, Itoigawa City, Niigata 949‐0393, Japan;2. Department of Material and Life Science, Graduate School of Engineering, Osaka University, SORST, Japan Science and Technology Agency (JST), Suita, Osaka 565‐0871, Japan |
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Abstract: | A mechanistic study on the Nieuwland catalysis for dimerization of acetylene is performed by detecting copper–acetylene and copper–monovinylacetylene π‐complexes and also by examining the kinetics under virtually the same reaction conditions employed in the industrial process. An efficient H/D exchange occurs between acetylene and protons in the Nieuwland catalytic system. Addition of a coordinating ligand to the conventional Nieuwland catalytic system results in improvement of the catalytic activity and selectivity for the acetylene dimerization. The kinetic analysis including the kinetic deuterium isotope effect provides valuable insight into the Nieuwland catalytic mechanism of the dimerization of acetylene. Copyright © 2008 John Wiley & Sons, Ltd. |
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Keywords: | copper complex acetylene Nieuwland catalyst H/D exchange |
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