Photoelectrochemical Conversion of Dinitrogen to Benzonitrile: Selectivity Control by Electrophile- versus Proton-Coupled Electron Transfer.

Nitride complexes are key species in homogeneous nitrogen fixation to NH via stepwise proton-coupled electron transfer (PCET). In contrast, direct generation of nitrogenous organic products from N -derived nitrides requires new strategies to enable efficient reductive nitride transfer in the presence of organic electrophiles. We here present a 2-step protocol for the conversion of dinitrogen to benzonitrile.

Epidermal Growth Factor Signaling Promotes Sleep through a Combined Series and Parallel Neural Circuit.

Sleep requires sleep-active neurons that depolarize to inhibit wake circuits. Sleep-active neurons are under the control of homeostatic mechanisms that determine sleep need. However, little is known about the molecular and circuit mechanisms that translate sleep need into the depolarization of sleep-active neurons.

First-Row Transition Metal (De)Hydrogenation Catalysis Based On Functional Pincer Ligands.

The use of 3d metals in de/hydrogenation catalysis has emerged as a competitive field with respect to "traditional" precious metal catalyzed transformations. The introduction of functional pincer ligands that can store protons and/or electrons as expressed by metal-ligand cooperativity and ligand redox-activity strongly stimulated this development as a conceptual starting point for rational catalyst design. This review aims at providing a comprehensive picture of the utilization of functional pincer ligands in first-row transition metal hydrogenation and dehydrogenation catalysis and related synthetic concepts relying on these such as the hydrogen borrowing methodology.

Phosphine-Stabilized Borylenes and Boryl Anions as Ligands? Redox Reactivity in Boron-Based Pincer Complexes.

Stabilized borylenes (L BH:) with weakly π-accepting substituents L, such as phosphines, were previously believed to be unstable. In the current manuscript, we describe a series of complexes formally containing a phosphine-stabilized borylene or boryl anion. In contrast to common trivalent boron compounds, the boron-based ligands in this study act as electron-donating ligands.

Proton Affinities of Cationic Carbone Adducts [AC(PPh3 )2 ](+) (A=Halogen, Hydrogen, Methyl) and Unusual Electronic Structures of the Cations and Dications [AC(H)(PPh3 )2 ](2.).

This work reports the syntheses and the first crystal structures of the cationic carbone adducts [FC(PPh3 )2 ](+) and [BrC(PPh3 )2 ](+) and the protonated dication [FC(H)(PPh3 )2 ](2+) , which are derived from the carbone C(PPh3 )2 . Quantum chemical calculations and bonding analyses were carried out for the series of cations [AC(PPh3 )2 ](+) and dications [AC(H)(PPh3 )2 ](2+) , where A=H, Me, F, Cl, Br, I. The bonding analysis suggests that the cations are best described as phosphane complexes L→(CA)(+) ←L (L=PPh3 ), which are related to the neutral borylene adducts L→(BA)←L (L=cyclic carbene; A=H, aryl) that were recently isolated.