Alex A, Clark T (1992)
Publication Status: Published
Publication Type: Journal article
Publication year: 1992
Publisher: American Chemical Society
Book Volume: 114
Pages Range: 506-510
Journal Issue: 2
DOI: 10.1021/ja00028a016
The 2s + 2s cycloaddition of ethylene, a forbidden Woodward-Hoffmann type closed-shell reaction, is illustrated by ab initio calculations to be catalyzed by complexation with Be.+. The reaction path calculated proceeds via a metallacyclopentane radical cation intermediate and two successive 1,2-hydrogen shifts to form the isomeric butenes. The possible reaction to cyclobutane by formation of a second carbon-carbon bond from the metallacyclopentane has also been examined. The complexed dimerization reaction is found to be exothermic for all products (26.3 kcal mol-1 for 1-butene, 27.9 kcal mol-1 for cis-2-butene, 29.5 kcal mol-1 for trans-2-butene, and 21.3 kcal mol-1 for cyclobutane) with no point on any of the reaction paths higher in energy than the starting point, Be.+ + 2C2H4. Remarkable parallels to transition-metal-catalyzed dimerizations are found.
APA:
Alex, A., & Clark, T. (1992). CATALYSIS OF ETHYLENE DIMERIZATION BY COMPLEXATION WITH METAL RADICAL CATIONS - AN ABINITIO STUDY. Journal of the American Chemical Society, 114(2), 506-510. https://doi.org/10.1021/ja00028a016
MLA:
Alex, Alexander, and Timothy Clark. "CATALYSIS OF ETHYLENE DIMERIZATION BY COMPLEXATION WITH METAL RADICAL CATIONS - AN ABINITIO STUDY." Journal of the American Chemical Society 114.2 (1992): 506-510.
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