Ferrocenylketene and ferrocenyl-1,2-bisketenes: direct observation and reactivity measurements |
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Authors: | Aguilar-Aguilar Angelica Allen Annette D Cabrera Eduardo Peña Fedorov Andrei Fu Nanyan Henry-Riyad Huda Leuninger Jörg Schmid Ulrich Tidwell Thomas T Verma Rishi |
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Affiliation: | Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6 Canada. |
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Abstract: | [Structure: see text]. Ferrocenylketene (1) is calculated to be destabilized by 1.6 kcal/mol relative to phenylketene (10) by B3LYP isodesmic comparison to the corresponding alkenes. Ketene 1 generated by Wolff rearrangement in CH3CN is identified by the IR band at 2119 cm(-1) and has a rate constant for reaction with n-BuNH2 less than that for 10 by a factor of 5. 1,2-Bisferrocenyl-1,2-bisketene 18 and 1-ferrocenyl-2-trimethylsilyl-1,2-bisketene 21 were prepared by photochemical ring opening of the corresponding cyclobutenediones, and 18 undergoes rapid ring closure 67 times faster than the corresponding 1,2-diphenyl-1,2-bisketene, while bisketene 21 is longer lived than 18 by a factor of 3.2 x 10(4). |
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