Related Experiment Video
Updated: Nov 25, 2025
The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Acid-promoted hydride transfer from an NADH analogue to a Cr(iii)-superoxo complex via a proton-coupled hydrogen atom
Tarali Devi1, Yong-Min Lee1, Shunichi Fukuzumi2
1Department of Chemistry and Nano Science, Ewha Womans University, Seoul 03760, Korea. wwnam@ewha.ac.kr fukuzumi@chem.eng.osak-u.ac.jp.
Abstract:
The sequential transfer of an electron, a proton and an electron in a hydride transfer from dihydronicotinamide adenine dinucleotide (NADH) and its analogues has never been separated well. In addition, the effect of acids on hydride transfer from an NADH analogue to a metal-superoxo species has yet to be reported. We report herein the first example of an acid-promoted hydride transfer from an NADH analogue, 10-methyl-9,10-dihydroacridine (AcrH2), to a Cr(iii)-superoxo complex, [(TMC)CrIII(O2)]2+, in the presence of HOTf in MeCN at 233 K. The acid-promoted hydride transfer from AcrH2 to [(TMC)CrIII(O2)]2+ occurs via a proton-coupled hydrogen atom transfer from AcrH2 to [(TMC)CrIII(O2)]2+ to produce a radical cation (AcrH2˙+) with an inverse deuterium isotope effect (KIE) of 0.93(5). AcrH2˙+ decayed via a proton transfer from AcrH2˙+ to AcrH2 with a KIE of 2.0(1), followed by the reaction of 10-methylacridinyl radical (AcrH˙) with [(TMC)CrIII(H2O2)]3+ to produce a 10-methylacridinium ion (AcrH+) and [(TMC)CrIII]3+. This work provides valuable insights into the mechanism of hydride transfer of NADH analogues by metal-superoxo intermediates, such as the switchover of the reaction mechanism from a one-step to a separated multi-step pathway in the presence of an acid.
More Related Videos
10:52Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
10:21Developing Photosensitizer-Cobaloxime Hybrids for Solar-Driven H2 Production in Aqueous Aerobic Conditions
Published on: October 5, 2019
Related Concept Videos
00:55Nitriles to Amines: LiAlH4 Reduction
As shown below, the mechanism involves three steps. Firstly, the hydride ion acting as a nucleophile attacks the nitrile carbon to form an anion. In the second step, a second equivalent of the hydride ion attacks the anion to...
01:19Acid Halides to Alcohols: LiAlH4 Reduction
The mechanism proceeds in three steps. First, the nucleophilic hydride ion attacks the carbonyl carbon of the acid halide to form a tetrahedral intermediate. Next, the carbonyl group is re-formed, and the halide ion departs as a leaving group, generating an aldehyde. A second nucleophilic attack by the hydride yields an alkoxide ion, which, upon protonation, gives a primary alcohol as...
01:17Carboxylic Acids to Primary Alcohols: Hydride Reduction
02:04Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
01:10Aldehydes and Ketones with HCN: Cyanohydrin Formation Mechanism
01:26Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation reactions,...