From allenes to tetracenes: Syntheses, structures, and reactivity of the intermediates

Abstract

Each step of the conversion of a series of 9-alkynyl-9H-fluorenes into the corresponding fluorenylidene-allenes that dimerize and proceed sequentially via head-to-tail and tail-to-tail dialkylidene-cyclobutanes, en route to electroluminescent tetracenes, has been characterized X-ray crystallographically. Allenes possessing substituents of very different electronic and steric character, such as aryl, halogeno, silyl, phosphino, and ferrocenyl, exhibit novel and unexpected reactivity patterns. The silyl-allenes dimerize to yield 1,2-bis(fluorenylidene)cyclobutanes of intrinsic C2 symmetry as a result of the overlapping fluorenylidenes with their large wingspans. Thermal rearrangement of a bis(fluorenyl)-bis(trimethylsilyl)- diallene generates the tetrabenzo-quatercyclopentadiene, C60H 36, which represents 60 % of the C60 framework. An attempt to isolate a "push-pull" allene, whose central carbon possesses carbene character, was made by incorporating a cation-stabilizing substituent (ferrocenyl) and an aromatic anionic moiety (fluorenide) at the termini. However, the allene underwent facile dimerization to the very heavily congested 3,4-di(spirofluorenyl)-1,2-bis(ferrocenyl-chloromethylene)cyclobutane that exhibits a very long (1.65 Å) C(3)-C(4) bond. Extension of this chemistry to dibenzosuberenylidene-allenes led to a straightforward route to the hitherto difficultly available dibenz[c,d,h]azulene system. Moreover, the reaction of 5-phenylethynyl-5H-dibenzo[a,d]cyclohepten-5-ol with dicobalt octacarbonyl yielded, surprisingly, the first isolated example of a (μ-alkyne)Co 2(CO)5(η2-alkene)complex, the long-sought first intermediate in the proposed mechanism of the Pauson-Khand reaction (PKR). © 2009 IUPAC.