Metal dodecaborates, particularly lithium dodecaborate (Li₂B₁₂H₁₂), are promising ionic conductors, but their broader application is hindered by complex synthesis. Here, we report a facile solvothermal synthesis of Li₂B₁₂H₁₂ via the reaction of lithium borohydride (LiBH₄) with borane dimethyl sulfide complex (DMS·BH₃) in glyme solvents. This synthesis can be conveniently performed either in a Schlenk flask (with or without reflux) or in an autoclave, demonstrating high yields (up to 96%) and excellent purity. The enclosed system provided by the autoclave was shown to be more favorable for the synthesis of the B₁₂H₁₂^2- anion. A detailed mechanistic investigation utilizing ¹¹B nuclear magnetic resonance (¹¹B NMR) spectroscopy revealed the stepwise formation of B₂H₇^-, B₃H₈^-, B₉H₁₄^-, B₁₁H₁₄^-, and B₁₁H₁₃^2- intermediates. This synthetic strategy was successfully extended to other alkali metal dodecaborates (Na, K), and their glyme-coordinated complexes were characterized by single-crystal X-ray diffraction. Furthermore, we introduce a solvent-exchange approach using weakly coordinating solvents such as dimethyl sulfoxide (DMSO) or water, enabling simple and efficient desolvation, thereby offering a practical new approach to obtain anhydrous metal dodecaborates.

Ammonia is a leading chemical in the agriculture, industry, and energy sectors, whereas nitrates are undesirable pollutants with harmful effects on the environment. Nitrate reduction to ammonia offers an efficient and sustainable route to produce green ammonia from waste nitrates. In this context, single- and dual-atom catalysts are considered the most promising owing to their maximum atomic utilization, highly tunable electronic structure, and well-defined active sites. This review focuses on the mechanism of nitrate reduction on single- and dual-atom catalysts, critically discussing the choice of metal, the engineering of coordination environment, and the effects of heteroatom doping. It also elaborates key performance descriptors and relates them to catalyst structure; the influence of operating parameters is also shown to be critical in determining catalytic activity and selectivity. The review further discusses how density functional theory and computational studies aid in the design and understanding of the operation of such catalysts. Finally, challenges and future research directions are elaborated to set a roadmap for researchers in the field.

C(sp³)–H bond activation is widely recognized as a key area for the development of organic chemistry in the 21st century. However, its activation has long been a challenge for scientists. The advent of photochemistry has offered hope for addressing this challenge. Various radicals generated under light irradiation have emerged as versatile hydrogen atom transfer (HAT) agents, streamlining the C–H activation process while enabling excellent regioselectivity. Herein, we present a chlorine radical-mediated hydrogen atom abstraction approach conducted under pressurized carbon monoxide (40 bar), which successfully achieves the C–H bond activation and carbonylation of cyclohexane.