Zirconacyclopentadiene‐Annulated Polycyclic Aromatic Hydrocarbons

Abstract

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Advantages of Group 4 Metallocene Bis(trimethylsilyl)acetylene Complexes as Metallocene Sources Towards Other Synthetically used Systems

“…The intermediate zirconacyclopentadiene produced with an excess of benzoic acid further products of protodemetallation in high yields (Scheme 15). [67] These and the other reported examples present a highly efficient method to produce new PAH's via fused zirconacyclopentadienes and subsequent protodemetalation. The authors published very selective reactions and high yields with Cp 2 Zr (py)(η 2 -btmsa) and suggested its suitability for the preparation of even larger PAH's and graphene-type nanostructures.…”

“…This opens the way to a lot of other synthetically very interesting reactions. [53][54][55][56][57][58][59][60][61][62][63][64][65][66][67][68][69][70][71] The most spectacular example for unexpected results was the reaction of η 5 : η 1 -pentafulvene titanium complexes with the allylidenephosphorylide Ph 3 P=C(H)À C(H)=CH 2 , giving a titanabutatriene complex by a spontaneous double CÀ H bond activation via an intermediate Ph 3 P=C=C=CH 2 . After dimerization the titanabutatriene complex formed a binuclear zig-zag hexapentaene titanium complex (Scheme 9).…”

“…These gave several examples of zirconacyclopentadiene‐annulated PAH's with up to 16 fused rings and five zirconacyclopentadiene rings. Using this concept, several PAH's with exocyclic diene functional groups were obtained, involving a general strategy to obtain expanded helicene molecules of this type (Scheme ) …”

Thermodynamically Stable o‐Quinodimethane: Synthesis, Structure, and Reactivity

“…Herein, we demonstrate that cyclobutaphenanthrene E , efficiently prepared by the (2+2) cycloaddition of an aryne and ketene silyl acetal (KSA), underwent thermal isomerization to afford the corresponding ring‐opened isomer F as a relatively stable product, provided the hydroxy group on the four‐membered ring in E is protected using a suitable substituent [7, 8] . Moreover, structure of the isolated o ‐quinodimethane was characterized by X‐ray crystallographic analysis, and its reactivity was investigated through the trapping reaction with a transiently generated aryne to afford the structurally attractive tetrabenzopentacene.…”