Alex A, Clark T (1992)
Publication Status: Published
Publication Type: Journal article
Publication year: 1992
Publisher: American Chemical Society
Book Volume: 114
Pages Range: 10897-10902
Journal Issue: 27
DOI: 10.1021/ja00053a028
The ring opening and isomerization of cyclopropane are shown by ab initio calculations to be catalyzed by complexation with Be.+. The reactions proceed via a common metallacyclobutane radical cation intermediate formed in a reaction that is endothermic by 12.3 kcal mol-1 relative to the cyclopropane-Be.+ complex. From this intermediate, three alternative reaction paths were examined, two isomerizations to give a propene-Be.+ complex and a C-C bond cleavage forming a carbene-ethylene-Be.+ species. These reactions are found to be exothermic by 5.4 and 5.2 kcal mol-1 relative to the cyclopropane-Be.+ complex, respectively. The isomerization of cyclopropane to give propene is calculated to be exothermic by 8.0 kcal mol-1 (exptl 7.9 kcal mol-1). Remarkable parallels to transition-metal catalyzed reactions were found for all the reactions examined.
APA:
Alex, A., & Clark, T. (1992). CATALYSIS OF THE RING-OPENING AND ISOMERIZATION OF CYCLOPROPANE BY COMPLEXATION WITH METAL RADICAL CATIONS - AN ABINITIO STUDY. Journal of the American Chemical Society, 114(27), 10897-10902. https://dx.doi.org/10.1021/ja00053a028
MLA:
Alex, Alexander, and Timothy Clark. "CATALYSIS OF THE RING-OPENING AND ISOMERIZATION OF CYCLOPROPANE BY COMPLEXATION WITH METAL RADICAL CATIONS - AN ABINITIO STUDY." Journal of the American Chemical Society 114.27 (1992): 10897-10902.
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