Related Experiment Video
Updated: Dec 31, 2025
The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Mechanistic diversity in acetophenone transfer hydrogenation catalyzed by ruthenium iminophosphonamide complexes
Alexander M Kalsin1, Tatyana A Peganova1, Iana S Sinopalnikova2
1A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov str., 119991 Moscow, Russia.
Abstract:
A series of arene ruthenium iminophosphonamide complexes, [(Arene)RuCl{R2P(NR')2}] (1), bearing various arenes and R,R' substituents on the NPN ligand have been investigated as precatalysts in acetophenone transfer hydrogenation in basic and base-free isopropanol. The results clearly demonstrate the presence of two distinct reaction mechanisms, which are controlled by the basicity of the N-atoms. Complexes 1 in which both R' substituents are aryl groups are only active once the neutral hydride complex [(Arene)RuH{R2P(NR')2}] (2) is generated in basic isopropanol, the latter being able to reduce a ketone via a stepwise hydride and proton transfer. On the other hand, complexes in which at least one R' group is Me readily catalyze the reaction in the absence of base. In the latter case, the results of kinetic studies and DFT calculations support an outer-sphere concerted asynchronous hydride and proton transfer assisted by the basic N-atom of the NPN ligand, which promotes catalysis via precoordination of an alcohol molecule by hydrogen bonding.
More Related Videos
10:39Heterogeneous Removal of Water-Soluble Ruthenium Olefin Metathesis Catalyst from Aqueous Media Via Host-Guest Interaction
Published on: August 23, 2018
06:46Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Related Concept Videos
02:17Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
02:24Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
02:36Regioselectivity and Stereochemistry of Hydroboration
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
02:13Reduction of Alkenes: Catalytic Hydrogenation
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...
02:34Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration
02:47Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.