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Carbonium Ion Stabilization by Metallocene Nuclei. II. α-Metallocenylcarbonium Ions

Hill, E. Alexander and Richards, John H. (1961) Carbonium Ion Stabilization by Metallocene Nuclei. II. α-Metallocenylcarbonium Ions. Journal of the American Chemical Society, 83 (18). pp. 3840-3846. ISSN 0002-7863. doi:10.1021/ja01479a025.

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Acetates of methylferrocenylcarbinol, methylruthenocenylcarbinol and methylosmocenylcarbinol have been found to solvolyze with rates somewhat greater than trityl acetate, indicating a high stability for the corresponding carbomum ions. The solvolysis mechanism for methylferrocenylcarbinyl acetate has been carefully investigated to show that a carbonium ion mechanism is involved. Several possibilities for a molecular orbital description of direct metal participation are discussed. The order for carbonium ion stabilization (osmocenyl > ruthenocenyl > ferrocenyl) is found to parallel that of the strength of intramolecular hydrogen bonds to the carbinols, but is the reverse of that observed for reactivity of the parent metallocene toward acetylation.

Item Type:Article
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Additional Information:© 1961 American Chemical Society. Received February 28, 1961.
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Caltech Gates and Crellin Laboratories of Chemistry2667
Issue or Number:18
Record Number:CaltechAUTHORS:20150429-085400147
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Official Citation:Carbonium Ion Stabilization by Metallocene Nuclei. II. α-Metallocenylcarbonium Ions E. Alexander Hill and John H. Richards Journal of the American Chemical Society 1961 83 (18), 3840-3846 DOI: 10.1021/ja01479a025
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:57080
Deposited By: Tony Diaz
Deposited On:01 May 2015 17:18
Last Modified:10 Nov 2021 21:07

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