Highly Nucleophilic Pyridinamide Anions in Apolar Organic Solvents due to Asymmetric Ion Pair Association.

Free ions in organic solvents of low polarity would be valuable tools for the activation of low-reactivity substrates. However, the formation of unreactive ion pairs at concentrations relevant for synthesis has prevented the success of this concept so far. On the example of highly nucleophilic pyridinamide phosphonium salts in dichloromethane, we show that asymmetric aggregation offers a solution to this general problem.

Ionic Conductivity Measurements-A Powerful Tool for Monitoring Polyol Reduction Reactions.

The reduction of metal precursors during the polyol synthesis of metal nanoparticles was monitored by ex situ ionic conductivity measurements. Using commonly used platinum precursors (KPtCl, HPtCl, and KPtCl) as well as iridium and ruthenium precursors (IrCl and RuCl), we demonstrate that their reduction in ethylene glycol at elevated temperatures is accompanied by a predictable change in ionic conductivity, enabling a precise quantification of the onset temperature for their reduction. This method also allows detecting the onset temperature for the further reaction of ethylene glycol with HCl produced by the reduction of chloride-containing metal precursors (at ≈120 °C).