Room Temperature Regioselective Catalytic Hydrodefluorination of Fluoroarenes with trans‐[Ru(NHC)4H2] through a Concerted Nucleophilic Ru−H Attack Pathway. Issue 6 (9th January 2017)

• Record Type: Journal Article
• Authors: Cybulski, Mateusz K.; McKay, David; Macgregor, Stuart A.; Mahon, Mary F.; Whittlesey, Michael K.
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 6(2017)
• Page Start: 1515
• Page End: 1519
• Publication Date: 2017-01-09
• Subjects: density functional calculations -- homogeneous catalysis -- hydrodefluorination -- N-heterocyclic carbenes -- ruthenium; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201610820
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The efficient and highly selective room temperature hydrodefluorination (HDF) of fluoroarenes by the trans‐[Ru(IMe4 )4 H2 ] catalyst, 3, is reported. Mechanistic studies show 3 acts directly in catalysis without any ligand dissociation and DFT calculations indicate a concerted nucleophilic attack mechanism. The calculations fully account for the observed selectivities which corroborate earlier predictions regarding the selectivity of HDF. Abstract : The reason for selectivity : Efficient and selective hydrodefluorination of fluoroarenes by a trans ‐[Ru(NHC)4 H2 ] catalyst is reported. DFT calculations indicate that the observed selectivities are fully consistent with a concerted nucleophilic attack mechanism without any prior ligand dissociation.