Stirring-Free Scalable Electrosynthesis Enabled by Alternating Current.

Alternating current (AC) electrolysis is receiving increased interest as a versatile tool for mild and selective electrochemical transformations. This work demonstrates that AC can enable the concept of a stirring-free electrochemical reactor where the periodic switch of electrode polarity, inherent to AC, provides uniform electrolysis across the whole volume of the reactor. Such design implies a straightforward approach for scaling up electrosynthesis.

Nucleophilic Substitution Reactions in the [BH] Anion in the Presence of Lewis Acids.

As a result of our study on the interaction between the octahydrotriborate anion with nucleophiles (Nu = THF, PhP, PhP-(CH)-PPh (dppe), PhAs, EtN, PhNH, CHN, CHCN, PhCHCN)) in the presence of a wide range of Lewis acids (Ti(IV), Hf(IV), Zr(IV), Al, Cu(I), Zn, Mn(II), Co(II) halides and iodine), a number of substituted derivatives of the octahydrotriborate anion [BHNu] are obtained. It is found that the use of TiCl, AlCl, ZrCl, HfCl, CuCl and iodine leads to the highest product yields. In this case, it is most likely that the reaction proceeds through the formation of an intermediate [BH-HMXn], which was detected by NMR spectroscopy.

Synthesis of Hafnium(IV) Polyaminoacetates.

The interaction of hafnium(IV) salts (oxide-dichloride, chloride, and bromide) with nitrilotriacetic acid (NTA), diethylenetriamminepentaacetic acid (DTPA), 1,2-diaminocyclohexanetetraacetic acid (CDTA), 1,3-dipropylmino-2-hydroxy ,,','-tetraacetic acid (dpta), and -(2-hydroxyethyl)ethylenediamine triacetic acid (HEDTA) has been studied. The corresponding complexes Na[Hf(NTA)]·3HO (), Na[HfDTPA]·3HO (), [HfCDTA(HO)] (), and Na[Hf(dpta)]·7.5HO·0.

Coupling of Alternating Current to Transition-Metal Catalysis: Examples of Nickel-Catalyzed Cross-Coupling.

The coupling of transition-metal to photoredox catalytic cycles through single-electron transfer steps has become a powerful tool in the development of catalytic processes. In this work, we demonstrated that transition-metal catalysis can be coupled to alternating current (AC) through electron transfer steps that occur periodically at the same electrode. AC-assisted Ni-catalyzed amination, etherification, and esterification of aromatic bromides showed higher yields and selectivity compared to that observed in the control experiments with direct current.