Diels-Alder Additions as Mechanistic Probes–Interception of Silyl-Isoindenes: Organometallic Derivatives of Polyphenylated Cycloheptatrienes and Related Seven-Membered Rings

Abstract

The intermediacy of short-lived isoindenes, generated in the course of metallotropic or silatropic shifts over the indene skeleton, can be shown by Diels-Alder trapping with tetracyanoethylene, leading to the complete elucidation of the dynamic behaviour of a series of polyindenylsilanes. Cyclopentadienones, bearing ferrocenyl and multiple phenyl or naphthyl substituents undergo [4 + 2] cycloadditions with diaryl acetylenes or triphenylcyclopropene to form the corresponding polyarylbenzenes or cycloheptatrienes. The heptaphenyltropylium cation, [C7Ph7+], was shown to adopt a nonplanar shallow boat conformation. In contrast, the attempted Diels-Alder reaction of tetracyclone and phenethynylfluorene yielded electroluminescent tetracenes. Finally, benzyne addition to 9-(2-indenyl)anthracene, and subsequent incorporation of a range of organometallic fragments, led to development of an organometallic molecular brake.

Keywords

• isoindenes
• tetracyanoethylene
• ferrocenylhexaphenylcycloheptatriene
• tropylium ions
• hexanaphthylbenzene
• X-ray crystallography