Ferrocenylketene and ferrocenyl-1,2-bisketenes: Direct observation and reactivity measurements

被引：32

作者：

Aguilar-Aguilar, A

Allen, AD

Cabrera, EP

Fedorov, A

Fu, NY

Henry-Riyad, H

Leuninger, J

Schmid, U

Tidwell, TT ^{[1
]}

Verma, R

机构：

[1] Univ Toronto, Dept Chem, Toronto, ON M5S 3H6, Canada

[2] Univ Guanajuato, Fac Quim, Guanajuato 36050, Mexico

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2005年 / 70卷 / 23期

关键词：

D O I：

10.1021/jo0515677

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

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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页码：9556 / 9561

页数：6

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