Hybrid Inorganic–Organic Cross-Metathesis between Diborenes and Acetylene
| Autor: | Benedikt Ritschel, Julian Böhnke, Holger Braunschweig, Marcel Härterich, Ashwini K. Phukan, Merle Arrowsmith, Ivo Krummenacher |
|---|---|
| Rok vydání: | 2021 |
| Předmět: |
chemistry.chemical_classification
Double bond 010405 organic chemistry Alkene Alkyne General Chemistry 010402 general chemistry Metathesis Triple bond 01 natural sciences Biochemistry Catalysis 0104 chemical sciences chemistry.chemical_compound Colloid and Surface Chemistry chemistry Acetylene Polymer chemistry Salt metathesis reaction Carbene |
| Zdroj: | Journal of the American Chemical Society. 143:18339-18345 |
| ISSN: | 1520-5126 0002-7863 |
| Popis: | The ruthenium-catalyzed cross-metathesis of alkenes and alkynes, which splits the alkene C═C double bond and couples one-half to each carbon of the alkyne C≡C triple bond, is one of the most efficient tools for the synthesis of 1,3-dienes, with wide-ranging applications, including pharmaceutical and polymer chemistry. In contrast, inorganic main-group metathesis reactions are restricted to a handful of examples of heavier p-block multiple bonds (P═P, Ge═Ge, and E≡E, E = Ge, Sn, Pb). We now report the first examples of thermally induced, transition-metal-free cross-metathesis between an organic alkyne and inorganic cyclic alkyl(amino)carbene (CAAC)-stabilized B═B double bonds, which yield fully planar, π-delocalized 1,8-diaza-3,6-diboraoctatetraenes. Density functional theory studies show that these compounds have an open-shell singlet biradical ground state with a thermally accessible closed-shell state. In-depth computational mechanistic analyses show that they are formed via a biradical cycloaddition-cycloreversion mechanism. Finally, unlike their organic counterparts, these B,N-analogues of octatetraene can undergo two-electron chemical reduction to form diamagnetic dianions. |
| Databáze: | OpenAIRE |
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