Article
Tuning the Reactivity of an Actor Ligand for Tandem CO2 and C–H Activations: From Spectator Metals to Metal-Free
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Davenport Chemical Research Laboratories, Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, Canada, M5S 3H6
J. Am. Chem. Soc., Article ASAP
DOI: 10.1021/ja4073832
Publication Date (Web): September 26, 2013
Copyright © 2013 American Chemical Society
Abstract
The 4,5-diazafluorenide ligand (L–) serves as an actor ligand in the formal insertion of CO2into a C–H bond remote from the metal center. With the Ru(II) complex of L– as the starting point, Rh(III), Rh(I), and Cu(I) were used as spectator metal centers to tune the reactivity of the actor ligand toward CO2. In the case of Rh(III)-diazafluorenide a room temperature reversible activation of CO2 was observed, similar to the isoelectronic Ru(II) analogue. In the case of Rh(I)- and Cu(I)-diazafluorenide CO2 is trapped by the formation of dinuclear carboxylate complexes and diazafluorene (LH). The spectator metal center could even be replaced entirely with an organic group allowing for the first metal-free reversible tandem CO2 and C–H activation.
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