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CAAC‐Based Thiele and Schlenk Hydrocarbons

Avijit Maiti, Jessica Stubbe, Nicolás I. Neuman, Pankaj Kalita, Prakash Duari, Carola Schulzke, Vadapalli Chandrasekhar, Biprajit Sarkar, Anukul Jana

2020Angewandte Chemie International Edition46 citationsDOIOpen Access PDF

Abstract

Diradicals have been of tremendous interest for over a century ever since the first reports of p- and m-phenylene-bridged diphenylmethylradicals in 1904 by Thiele and 1915 by Schlenk. Reported here are the first examples of cyclic(alkyl)(amino)carbene (CAAC) analogues of Thiele's hydrocarbon, a Kekulé diradical, and Schlenk's hydrocarbon, a non-Kekulé diradical, without using CAAC as a precursor. The CAAC analogue of Thiele's hydrocarbon has a singlet ground state, whereas the CAAC analogue of Schlenk's hydrocarbon contains two unpaired electrons. The latter forms a dimer, by an intermolecular double head-to-tail dimerization. This straightforward synthetic methodology is modular and can be extended for the generation of redox-active organic compounds.

Topics & Concepts

DiradicalChemistryDimerHydrocarbonAlkylSinglet stateCarbeneComputational chemistryOrganic chemistryCatalysisPhysicsNuclear physicsExcited stateSynthesis and Properties of Aromatic CompoundsN-Heterocyclic Carbenes in Organic and Inorganic ChemistryCoordination Chemistry and Organometallics
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