A versatile synthetic strategy for the preparation of homo- and heterobimetallic complexes bearing an unprecedented mesoionic Janus-type diNHC is presented. Moreover, its electronic property is evaluated, and a preliminary catalytic application in the direct diarylation of 1-methylpyrrole is demonstrated.
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Mesoionic Janus-Type Dicarbene: Complexes, Adducts, and Catalytic Studies.
Chemistry
September 2024
Department of Chemistry, Faculty of Science, National University of Singapore, 3 Science Drive 3, Singapore, 117453, Republic of Singapore.
The preparations of homo- and hetero-bimetallic complexes as well as thiourea and selenourea derivatives of a mesoionic Janus-type N-heterocyclic dicarbene (diNHC) are reported. Analogues of its monocationic intermediate NHC have also been obtained for comparison. Using the main group adducts, the π-acceptor properties of both NHCs were determined using low temperature Se NMR spectroscopy completing their stereoelectronic profiling.
View Article and Find Full Text PDFDesign of a Mesoionic Janus-type Dicarbene.
J Am Chem Soc
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Department of Chemistry, Faculty of Science, National University of Singapore, 3 Science Drive 3, Singapore 117453, Republic of Singapore.
A versatile synthetic strategy for the preparation of homo- and heterobimetallic complexes bearing an unprecedented mesoionic Janus-type diNHC is presented. Moreover, its electronic property is evaluated, and a preliminary catalytic application in the direct diarylation of 1-methylpyrrole is demonstrated.
View Article and Find Full Text PDFOn the dual reactivity of a Janus-type mesoionic dipole: experiments and theoretical validation.
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Departamento de Química Orgánica e Inorgánica, Facultad de Ciencias-UEX, IACYS-Unidad de Química Verde y Desarrollo Sostenible, E-06006 Badajoz, Spain.
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Institute for Advanced Study (USIAS), and Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, 67081 Strasbourg Cedex, France.
The first direct observation of the tautomeric equilibrium between mesoionic imidazolium aminides (IA) and amino NHCs (AC) shows its dependence on the aminide substituent. A potassium (imidazol-2-ylidenyl)(anilide), an ion-pair with the 'free' anionic NHC, and potassium organometallic polymers, with the repeat unit exhibiting 'Janus-type' coordination, are reported.
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