Direct Amination of Benzene with Molecular Nitrogen Enabled by Plasma‐Liquid Interactions

Atmospheric reactions and slow geological processes controlled Earth's earliest nitrogen cycle, and by ~2.7 billion years ago, a linked suite of microbial processes evolved to form the modern nitrogen cycle with robust natural feedbacks and controls. Over the past century, however, the development of new agricultural practices to satisfy a growing global demand for food has drastically disrupted the nitrogen cycle. This has led to extensive eutrophication of fresh waters and coastal zones as well as increased inventories of the potent greenhouse gas nitrous oxide (N(2)O). Microbial processes will ultimately restore balance to the nitrogen cycle, but the damage done by humans to the nitrogen economy of the planet will persist for decades, possibly centuries, if active intervention and careful management strategies are not initiated. Show more

Pd-catalyzed cross-coupling reactions that form C–N bonds have become useful methods to synthesize anilines and aniline derivatives, an important class of compounds throughout chemical research. A key factor in the widespread adoption of these methods has been the continued development of reliable and versatile catalysts that function under operationally simple, user-friendly conditions. This review provides an overview of Pd-catalyzed N-arylation reactions found in both basic and applied chemical research from 2008 to the present. Selected examples of C–N cross-coupling reactions between nine classes of nitrogen-based coupling partners and (pseudo)aryl halides are described for the synthesis of heterocycles, medicinally relevant compounds, natural products, organic materials, and catalysts. Show more

Dinitrogen (N2) was reduced to ammonia at room temperature and 1 atmosphere with molybdenum catalysts that contain tetradentate [HIPTN3N]3- triamidoamine ligands (such as [HIPTN3N]Mo(N2), where [HIPTN3N]3- is [(3,5-(2,4,6-i-Pr3C6H2)2C6H3NCH2CH2)3N]3-) in heptane. Slow addition of the proton source [(2,6-lutidinium)(BAr'4), where Ar' is 3,5-(CF3)2C6H3]and reductant (decamethyl chromocene) was critical for achieving high efficiency ( approximately 66% in four turnovers). Numerous x-ray studies, along with isolation and characterization of six proposed intermediates in the catalytic reaction under noncatalytic conditions, suggest that N2 was reduced at a sterically protected, single molybdenum center that cycled from Mo(III) through Mo(VI) states. Show more