title: Electrocyclic reactions of siloles: a combined experimental and theoretical study.
abstract: The reaction of 4-chloro-1,2-dimethyl-4-supersilylsila-1-cyclopentene (2 a) with Li[NiPr2] at -78 °C results in the formation of the formal 1,4-addition product of the silacyclopentadiene derivative 3,4-dimethyl-1-supersilylsila-1,3-cyclopentadiene (4 a) with 2,3-dimethyl-4-supersilylsila-1,3-cyclopentadiene (5 a). In addition the respective adducts of the Diels-Alder reactions of 4 a+4 a and 4 a+5 a were obtained. Compound 4 a, which displays an s-cis-silacyclopentadiene configuration, reacts with cyclohexene to form the racemate of the [4+2] cycloadduct of 4 a and cyclohexene (9). In the reaction between 4 a and 2,3-dimethylbutadiene, however, 4 a acted as silene as well as silacyclopentadiene to yield the [2+4] and [4+2] cycloadducts 10 and 11, respectively. The constitutions of 9, 10, and 11 were confirmed by NMR spectroscopy and their crystal structures were determined. Reaction of 4-chloro-1,2-dimethyl-4-tert-butyl-4-silacyclopent-1-ene (2 c) with KC8 yielded the corresponding disilane (12), which was characterized by X-ray crystal structure analysis (triclinic, P1). DFT calculations are used to unveil the mechanistic scenario underlying the observed reactivity.
authors.affiliation: Institut für Anorganische und Analytische Chemie, Goethe-Universität, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main (Germany), Fax: (+49) 69-798-29260.
authors.forename: Frank
authors.initials: F
authors.lastname: Meyer-Wegner
authors.forename: Josef H
authors.initials: JH
authors.lastname: Wender
authors.forename: Konstantin
authors.initials: K
authors.lastname: Falahati
authors.forename: Timo
authors.initials: T
authors.lastname: Porsch
authors.forename: Tanja
authors.initials: T
authors.lastname: Sinke
authors.forename: Michael
authors.initials: M
authors.lastname: Bolte
authors.forename: Matthias
authors.initials: M
authors.lastname: Wagner
authors.forename: Max C
authors.initials: MC
authors.lastname: Holthausen
authors.forename: Hans-Wolfram
authors.initials: HW
authors.lastname: Lerner
keywords: cycloaddition; density functional calculations; electrocyclic reactions; reaction mechanisms; siloles