Related Experiment Video
Updated: Nov 3, 2025

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
Experimental and theoretical studies on gold(III) carbonyl complexes: reductive C,H- and C,C bond formation
Alexander Ahrens1, Danilo M Lustosa2, Leonhard F P Karger1
1Organisch-Chemisches Institut, Heidelberg University, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany. hashmi@hashmi.de.
Abstract:
The reactivity of cationic (C^C)gold(iii) carbonyl complexes was investigated. While the in situ-formed IPrAu(bph)CO+ complex (bph = biphenyl-2,2'-diyl) does not undergo a migratory insertion of CO into the neighboring gold-carbon bond, nucleophiles can attack the coordinated CO moiety intermolecularly. Water as a nucleophile initiates a CO2 extrusion combined with a reductive C,H bond formation. The rapid formation of a gold(i) species from an intermediary gold(iii) carbonyl has not been observed before and shows a significant difference in reactivity between (C^C) and (C^N^C)gold(iii) carbonyls. The latter have been reported to form stable gold(iii) hydrides via the WGS reaction. In the case of methanol acting as a nucleophile attacking the gold(iii) carbonyl, no extrusion of CO2 is observed. Instead an intermediary gold(iii) carboxyl complex forms an aryl carboxylate via reductive C-C bond elimination. Experimental and theoretical studies on the mechanism explain the observed selectivities and give new insights into the reactivity of elusive gold(iii) carbonyls.
More Related Videos
06:34Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides CHIPS
Published on: June 20, 2014
06:31Preparation of SNS CobaltII Pincer Model Complexes of Liver Alcohol Dehydrogenase
Published on: March 19, 2020
Related Concept Videos
Aldehydes and Ketones with HCN: Cyanohydrin Formation Mechanism
Aldehydes and Ketones with HCN: Cyanohydrin Formation Overview
Alcohols from Carbonyl Compounds: Reduction
Catalytic hydrogenation is similar to the reduction of an alkene or alkyne by adding H2 across the pi bond in the presence of transition metal catalysts like Raney Ni, Pd–C, Pt, or Ru. Aldehydes and ketones can be reduced by this method, often under mild to moderate heat (25–100°C) and...
Acid Halides to Ketones: Gilman Reagent
As shown below, the mechanism proceeds in two steps. First, one of the alkyl groups of the reagent acts as a nucleophile and attacks the acyl carbon of the acid chloride to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen...
Properties of Organometallic Compounds
Preparation of Aldehydes and Ketones from Carboxylic Acid Derivatives
Carboxylic acid derivatives like acid chlorides and esters are more easily reducible than the corresponding acids. The derivatives reduce in the presence of mild reducing agents to give aldehydes. Aldehydes can also be prepared by Rosenmund reduction, that is, the reduction of...