Missing Reactivity of Trimethylsilyl Reagents: Dehalogenative Activation Enabling One-Pot Generation of Aryne from 2-Iodophenol

Herein we present a missing reactivity of trimethylsilyl reagents; dehalogenative activation, which involves abstracting a halogen atom and anionically activating the substrate similar to the halogen-metal exchange reaction in classical carbanion species. This missing reactivity allowed for the one-pot generation of aryne from 2-iodophenol.

Missing Reactivity of Trimethylsilyl Reagents: Dehalogenative Activation Enabling One-Pot Generation of Aryne from 2-Iodophenol

Herein we present a missing reactivity of trimethylsilyl reagents; dehalogenative activation, which involves abstracting a halogen atom and anionically activating the substrate similar to the halogen-metal exchange reaction in classical carbanion species. This missing reactivity allowed for the one-pot generation of aryne from 2-iodophenol.

Intramolecular Metal Exchange Reaction Promoted by Thiol Ligands

The synthesis of an alloy nanocluster that is atomically precise is the key to understanding the metal synergy effect at the atomic level. Using the Ag2Au25(SR)18 nanocluster as a model, we reported a third approach for the metal exchange reaction, that is, intramolecular metal exchange. The surface adsorbed metal ions (i.e., Ag) can be exchanged with the kernel metal atoms (i.e., Au) that are promoted by thiol ligands. The exchanged gold atoms can be further stripped by the thiol ligands, and produce the AgxAu25−x(SR)18− nanocluster.

STUDY OF CADMIUM OCTA(4-METHOXYPHENYL)PORPHYRINATE IN REACTION OF METAL EXCHANGE WITH TIN CHLORIDE IN DMF

Metal-exchange reaction for complexes with macrocyclic ligands refers to a special type of complex coordination interactions. The reaction of metal exchange has founded wide application for the synthesis of complexes of natural and synthetic porphyrins. In the general form, the metal-exchange reaction may be written as follows:MР + M/Xn(Solv)m-n® M/Р + MXn(Solv)m-nwhere МP and M/P are metalloporphyrins, M/Xn(Solv)m-n are metal salts of solvate complexes. Cd-octa(4-methoxyphenyl)porphyrin was obtained by the reaction of octa(4-methoxyphenyl)-porphyrin-ligand with cadmium chloride in the presence of potassium acetate in dime-thylformamide. The obtained compound was identified by the methods of UV-VIS spectroscopy, 1H NMR and mass-spectrometry. The reaction order on the salt and the complex of cadmium in the case of the reactions of the Cd-octa(4-methoxyphenyl)porphyrin metal-exchange with tin chloride in dimethylformamide is equal to 1. Thus, the metal-exchange reaction is bimolecular and its total rate obeys to the second-order kinetic equation. It is suggested that the metal-exchange reaction of Cd-оcta(4-methoxyphenyl)porphyrin with tin chloride in dimethyl-formamide proceeds through a bimolecular associative mechanism.

On the mechanism of rapid metal exchange between thiolate-protected gold and gold/silver clusters: a time-resolved in situ XAFS study

The fast metal exchange reaction between Au38 and AgxAu38−x nanoclusters has been studied by time resolved in situ X-ray absorption spectroscopy.