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The First Crystal Structure of a Reactive Dirhodium Carbene Complex and a Versatile Method for the Preparation of Gold Carbenes by Rhodium‐to‐Gold Transmetalation

The dirhodium carbene derived from bis(4‐methoxyphenyl)diazomethane and [Rh(tpa)(4)]⋅CH(2)Cl(2) (tpa=triphenylacetate) was characterized by UV, IR, and NMR spectroscopy, HRMS, as well as by X‐ray diffraction. The isolated complex exhibits prototypical rhodium carbene reactivity in that it cyclopropa...

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Detalles Bibliográficos
Autores principales: Werlé, Christophe, Goddard, Richard, Fürstner, Alois
Formato: Online Artículo Texto
Lenguaje:English
Publicado: WILEY‐VCH Verlag 2015
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4832834/
https://www.ncbi.nlm.nih.gov/pubmed/26534892
http://dx.doi.org/10.1002/anie.201506902
Descripción
Sumario:The dirhodium carbene derived from bis(4‐methoxyphenyl)diazomethane and [Rh(tpa)(4)]⋅CH(2)Cl(2) (tpa=triphenylacetate) was characterized by UV, IR, and NMR spectroscopy, HRMS, as well as by X‐ray diffraction. The isolated complex exhibits prototypical rhodium carbene reactivity in that it cyclopropanates 4‐methoxystyrene at low temperature. Experimental structural information on this important type of reactive intermediate is extremely scarce and thus serves as a reference point for mechanistic discussions of rhodium catalysis in general. Moreover, dirhodium carbenes are shown to undergo remarkably facile carbene transfer on treatment with [LAuNTf(2)] (L=phosphine). This formal transmetalation opens a valuable new entry into gold carbene complexes that cannot easily be made otherwise; three fully characterized representatives illustrate this aspect.