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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

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Werlé,  Christophe
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Goddard,  Richard
Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Fürstner,  Alois
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Werlé, C., Goddard, R., & Fürstner, A. (2015). 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. Angewandte Chemie International Edition, 54(51), 15452-15456. doi:10.1002/anie.201506902.


Cite as: https://hdl.handle.net/11858/00-001M-0000-0029-643F-2
Abstract
The dirhodium carbene derived from bis(4-methoxyphenyl)diazomethane and [Rh(tpa)4]⋅CH2Cl2 (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 [LAuNTf2] (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.