Acylation of Hexaphenylbenzene for the Synthesis of [5]Cumulenes
Matthew A. Johnson
Department of Chemistry, University of Alberta, Edmonton, Alberta, T6G 2G2 Canada
Search for more papers by this authorDr. Max M. Martin
Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-University Erlangen-Nuernberg, Nikolaus-Fiebiger Str. 10, 91058 Erlangen, Germany
Search for more papers by this authorDr. Kévin Cocq
Department of Chemistry, University of Alberta, Edmonton, Alberta, T6G 2G2 Canada
Search for more papers by this authorProf. Dr. Norbert Jux
Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-University Erlangen-Nuernberg, Nikolaus-Fiebiger Str. 10, 91058 Erlangen, Germany
Search for more papers by this authorDr. Michael J. Ferguson
Department of Chemistry, University of Alberta, Edmonton, Alberta, T6G 2G2 Canada
Search for more papers by this authorCorresponding Author
Prof. Dr. Rik R. Tykwinski
Department of Chemistry, University of Alberta, Edmonton, Alberta, T6G 2G2 Canada
Search for more papers by this authorMatthew A. Johnson
Department of Chemistry, University of Alberta, Edmonton, Alberta, T6G 2G2 Canada
Search for more papers by this authorDr. Max M. Martin
Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-University Erlangen-Nuernberg, Nikolaus-Fiebiger Str. 10, 91058 Erlangen, Germany
Search for more papers by this authorDr. Kévin Cocq
Department of Chemistry, University of Alberta, Edmonton, Alberta, T6G 2G2 Canada
Search for more papers by this authorProf. Dr. Norbert Jux
Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-University Erlangen-Nuernberg, Nikolaus-Fiebiger Str. 10, 91058 Erlangen, Germany
Search for more papers by this authorDr. Michael J. Ferguson
Department of Chemistry, University of Alberta, Edmonton, Alberta, T6G 2G2 Canada
Search for more papers by this authorCorresponding Author
Prof. Dr. Rik R. Tykwinski
Department of Chemistry, University of Alberta, Edmonton, Alberta, T6G 2G2 Canada
Search for more papers by this authorGraphical Abstract
Hexaphenylbenzene is appended to [5]cumulenes, a marriage of sp- and sp2-carbon building blocks for synthetic allotropes.
Abstract
The Friedel-Crafts acylation of hexaphenylbenzene is reported, and the reaction favorably provides the monoacylated products 1 a and 1 b. The resulting ketones 1 a and 1 b are used as precursors for the formation of [5]cumulenes, including 6 b in which the sterically demanding HPB moiety affords a diethynyl[5]cumulene that features significant stability (persistence) versus the analog 6 c which lacks the HPB endgroups. The unsymmetrical substitution pattern of the two most soluble derivatives 6 b and 6 c, allows for estimation of rotational barriers for diethynyl[5]cumulenes via VT NMR studies of cis-trans isomerization. For both molecules, the barrier to rotation is ca. 15 kcal mol−1, which is attenuated in comparison to other [5]cumulenes due to the presence of the ethynyl endgroups.
Conflict of interest
The authors declare no conflict of interest.
Open Research
Data Availability Statement
The data that support the findings of this study are available from the corresponding author upon reasonable request.
Supporting Information
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