Transmetalation of Boronic Acids and their Derivatives: Mechanistic Elucidation and Relevance to Catalysis

The Suzuki–Miyaura reaction (cross-coupling reaction of boronic acids with organic halides catalysed by Pd complexes) has been recognised as the useful synthetic organic reaction that forms a C(sp2)–C(sp2) bond. The...

Salt-Enhanced Oxidative Addition of Iodobenzene to Pd: an Inter-play Between Cation, Anion and Pd-Pd Cooperative Effects

Halide salts facilitate the oxidative addition of organic halides to Pd(0). This phenomenon originates from a combina-tion of anionic, cationic and Pd-Pd cooperative effects. Exhaustive computational exploration at the DFT level of the com-plexes obtained from [Pd0(PPh3)2] and a salt (NMe4Cl or LiCl) showed that chlorides promote phosphine release, leading to a mixture of mononuclear and dinuclear Pd(0) complexes. Anionic Pd(0) dinuclear complexes exhibit a cooperativity between Pd(0) centers which favors the oxidative addition of iodobenzene. The higher activity of Pd(0) dimers toward oxidative addition rationalizes the previously reported kinetic laws. In the presence of Li+, the oxidative addition to mon-onuclear [Pd0L(Li2Cl2)] is estimated barrierless. LiCl coordination polarizes Pd(0), enlarging both the electrophilicity and the nucleophilicity of the complex, which promotes both coordination of the substrate and the subsequent insertion into the C-I bond. These conclusions are paving the way to the rational use of salt effect in catalysis for the activation of more challenging bonds.

Photoelectrocatalytic C–H halogenation over an oxygen vacancy-rich TiO2 photoanode

Photoelectrochemical cells are emerging as powerful tools for organic synthesis. However, they have rarely been explored for C–H halogenation to produce organic halides of industrial and medicinal importance. Here we report a photoelectrocatalytic strategy for C–H halogenation using an oxygen-vacancy-rich TiO2 photoanode with NaX (X=Cl−, Br−, I−). Under illumination, the photogenerated holes in TiO2 oxidize the halide ions to corresponding radicals or X2, which then react with the substrates to yield organic halides. The PEC C–H halogenation strategy exhibits broad substrate scope, including arenes, heteroarenes, nonpolar cycloalkanes, and aliphatic hydrocarbons. Experimental and theoretical data reveal that the oxygen vacancy on TiO2 facilitates the photo-induced carriers separation efficiency and more importantly, promotes halide ions adsorption with intermediary strength and hence increases the activity. Moreover, we designed a self-powered PEC system and directly utilised seawater as both the electrolyte and chloride ions source, attaining chlorocyclohexane productivity of 412 µmol h−1 coupled with H2 productivity of 9.2 mL h−1, thus achieving a promising way to use solar for upcycling halogen in ocean resource into valuable organic halides.

Application of α-Amino Radicals as the Reaction Activators

α-Aminoalkyl radicals are easily accessible through multiple pathways from various precursors. Apart from their utilization as N-containing building blocks, they have recently been used as halogen atom abstraction reagents or single-electron reductants to transform organic halides or sulfonium salts to their corresponding highly reactive radical species. Benefiting from the richness of various halides and the diverse reactivity of radical intermediates, new transformations of halides and sulfonium salts have been developed. This short review summarizes this emerging chemistry that uses α-amino radicals as the reaction activators.

Technoeconomic Assessment of Organic Halide Based Gold Recovery from Waste Electronic and Electrical Equipment

Waste Electronic and Electrical Equipment (WEEE) is one of the fastest growing waste streams worldwide, with significant economic value due to the precious metals contained within. Currently, only a small share of the total globally produced quantity produced is treated effectively and a large amount of valuable non-renewable resources are being wasted. Moreover, the methods currently applied in industry on a large scale are not always environmentally friendly. Thus, an economically viable and environmentally friendly method that would achieve high recovery of certain elements is sought. The objective of this paper is to assess four different organic halides as leaching agents for gold recovery from WEEE. Two of them have been previously tested (namely N-bromosuccinimide, NBS, and N-chlorosuccinimide, NCS) and have shown promising results, whereas the other two are novel and were selected due to their lower toxicity levels (trichloroisocyanuric acid, TCICA, and tribromoisocyanuric acid, TBICA). Both commercially supplied pure gold powder and WEEE dust from a recycling company were used as the gold source. Results show that from a technical standpoint, the NBS is a superior solution with both substrates, reaching 61% and 99% extraction efficiency from WEEE dust and pure gold, respectively. The other three methods recorded lower recovery efficiency (with the highest value reaching 36% for NCS, 53% for TCICA and 29% for TBICA). However, taking into account the price of gold and the expenses of the extraction process, only three of the lixiviants tested (NBS, NCS and TCICA) could be potentially profitable and viable on a larger scale.