title: Ferrocenylketene and ferrocenyl-1,2-bisketenes: direct observation and reactivity measurements.
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).
authors.affiliation: Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6 Canada.
authors.forename: Angelica
authors.initials: A
authors.lastname: Aguilar-Aguilar
authors.forename: Annette D
authors.initials: AD
authors.lastname: Allen
authors.forename: Eduardo Peña
authors.initials: EP
authors.lastname: Cabrera
authors.forename: Andrei
authors.initials: A
authors.lastname: Fedorov
authors.forename: Nanyan
authors.initials: N
authors.lastname: Fu
authors.forename: Huda
authors.initials: H
authors.lastname: Henry-Riyad
authors.forename: Jörg
authors.initials: J
authors.lastname: Leuninger
authors.forename: Ulrich
authors.initials: U
authors.lastname: Schmid
authors.forename: Thomas T
authors.initials: TT
authors.lastname: Tidwell
authors.forename: Rishi
authors.initials: R
authors.lastname: Verma