Unexpected Formation of a [4]Radialene and Dendralenes by Addition of Tetracyanoethylene to a Tetraaryl[5]cumulene†
Johanna A. Januszewski
Department für Chemie und Pharmazie & Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Henkestrasse 42, 91054 Erlangen (Germany) http://www.chemie.uni-erlangen.de/tykwinski
Search for more papers by this authorDr. Frank Hampel
Department für Chemie und Pharmazie & Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Henkestrasse 42, 91054 Erlangen (Germany) http://www.chemie.uni-erlangen.de/tykwinski
Search for more papers by this authorDr. Christian Neiss
Lehrstuhl für Theoretische Chemie & Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Egerlandstrasse 3, 91058 Erlangen (Germany)
Search for more papers by this authorProf. Dr. Andreas Görling
Lehrstuhl für Theoretische Chemie & Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Egerlandstrasse 3, 91058 Erlangen (Germany)
Search for more papers by this authorCorresponding Author
Prof. Dr. Rik R. Tykwinski
Department für Chemie und Pharmazie & Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Henkestrasse 42, 91054 Erlangen (Germany) http://www.chemie.uni-erlangen.de/tykwinski
Department für Chemie und Pharmazie & Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Henkestrasse 42, 91054 Erlangen (Germany) http://www.chemie.uni-erlangen.de/tykwinskiSearch for more papers by this authorJohanna A. Januszewski
Department für Chemie und Pharmazie & Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Henkestrasse 42, 91054 Erlangen (Germany) http://www.chemie.uni-erlangen.de/tykwinski
Search for more papers by this authorDr. Frank Hampel
Department für Chemie und Pharmazie & Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Henkestrasse 42, 91054 Erlangen (Germany) http://www.chemie.uni-erlangen.de/tykwinski
Search for more papers by this authorDr. Christian Neiss
Lehrstuhl für Theoretische Chemie & Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Egerlandstrasse 3, 91058 Erlangen (Germany)
Search for more papers by this authorProf. Dr. Andreas Görling
Lehrstuhl für Theoretische Chemie & Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Egerlandstrasse 3, 91058 Erlangen (Germany)
Search for more papers by this authorCorresponding Author
Prof. Dr. Rik R. Tykwinski
Department für Chemie und Pharmazie & Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Henkestrasse 42, 91054 Erlangen (Germany) http://www.chemie.uni-erlangen.de/tykwinski
Department für Chemie und Pharmazie & Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Henkestrasse 42, 91054 Erlangen (Germany) http://www.chemie.uni-erlangen.de/tykwinskiSearch for more papers by this authorFunding is gratefully acknowledged from the Friedrich-Alexander-Universität Erlangen-Nürnberg, the Deutsche Forschungsgemeinschaft (SFB 953, “Synthetic Carbon Allotropes”), and “Solar Technologies go Hybrid”—an initiative of the Bavarian State Ministry for Science, Research, and Art. We thank Dr. Alexandra Griffin (Agilent Technologies) for collecting the X-ray structure data of 10 a.
Graphical Abstract
Unusual structures and interesting electronic properties characterize the cyclic products from the reaction of TCNE with tetraaryl[5]cumulene. Mechanistic investigations, aided by DFT calculations, outline a likely pathway to the observed products. The addition of MeOH, EtOH, and Br2 to various intermediates leads to the interesting dendralene compounds.
Abstract
The use of cumulenes in synthetic transformations offers the possibility to form structurally interesting and potentially useful conjugated molecules. The cycloaddition reaction of a tetraaryl[5]cumulene with the electron-deficient olefin tetracyanoethylene affords unusual products, including functionalized dendralenes and alkylidene cyclobutanes, as well as a symmetric [4]radialene that shows unique solvatochromism, with λmax values approaching the near-IR region. These carbon-rich products have been investigated spectroscopically and by X-ray crystallographic analysis (five structures). The cycloaddition reaction sequence has also been explored by mechanistic and theoretical studies. The obtained results clearly demonstrate the potential of [5]cumulenes to serve as precursors for unprecedented conjugated structures.
Supporting Information
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