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Deuterium kinetic isotope effects and H/D exchange in dimerization of acetylene with a Nieuwland catalyst in aqueous media
Author(s) -
Tachiyama Takashi,
Yoshida Makoto,
Aoyagi Tatsuhiro,
Fukuzumi Shunichi
Publication year - 2008
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1373
Subject(s) - acetylene , chemistry , catalysis , kinetic isotope effect , deuterium , copper , aqueous solution , inorganic chemistry , photochemistry , organic chemistry , physics , quantum mechanics
Deuterium kinetic isotope effects were observed in the dimerization of acetylene with a Nieuwland catalyst in an aqueous media, where the copper–acetylene and copper–monovinylacetylene (MVA) π ‐complexes were detected as intermediates by 1 H NMR. The copper–acetylene π ‐complex is responsible for an efficient H/D exchange between acetylene and proton (or deuteron) of water, which occurs rapidly with a Nieuwland catalyst. The deuterium kinetic isotope effects and the rapid H/D exchange reaction together with the detection of the copper–acetylene and copper–MVA π ‐complexes provide deeper insight into the catalytic mechanism of the Nieuwland catalysis for the dimerization of acetylene. Copyright © 2008 John Wiley & Sons, Ltd.