Dianionic and Neutral Diboron-Centered Classical Diradicaloids.

Herein, we report the syntheses and electronic structures of crystalline dianionic as well as neutral diboron-centered classical diradicaloids as boron analogues of classical Thiele, Chichibabin, and Müller (this only for dianionic diradicaloids!) hydrocarbons. These are based on borane radical anion and NHC-stabilized boryl radical spin carriers, respectively. All these dianionic diboron-centered diradicaloids exhibit triplet population at room temperature regardless of the π-conjugated spacer: p-phenylene, p,p'-biphenylene, or p,p″-terphenylene. In the case of neutral diboron-centered diradicaloids, the employed π-conjugated spacer plays a crucial role for the triplet population at room temperature: EPR inactive for p-phenylene vs EPR active for p,p'-biphenylene. The findings emphasize the importance of the spin carriers for the resulting ground-state: borane radical anion vs NHC-stabilized boryl radical along with the pivotal role of the π-conjugated spacer as spin-coupler between two spins. Notably, 100 years (a century) after the first report by Krause of the triphenyl borane radical-anion, being isoelectronic to the triphenylmethyl radical, we convey borane radical anion-based diradicaloids. Furthermore, while donor-stabilized boryl radicals were introduced in the 1980s by Giles and Roberts, said concept is herewith being extended to NHC-stabilized boryl radical-based diradicaloids.

Reversal of Regioselectivity in Asymmetric C-H Bond Annulation with Bromoalkynes under Cobalt Catalysis.

Metal-catalyzed asymmetric C-H bond annulation strategy offers a versatile platform, allowing the construction of complex P-chiral molecules through atom- and step-economical fashion. However, regioselective insertion of π-coupling partner between M-C bond with high enantio-induction remain elusive. Using commercially available Co(II) salt and chiral-Salox ligands, we demonstrate an unusual protocol for the regio-reversal, enantioselective C-H bond annulation of phosphinamide with bromoalkyne through desymmetrization. The reaction proceeds through ligand-assisted enantiodetermining cyclocobaltation followed by regioselective insertion of bromoalkyne between Co-C, subsequent reductive elimination, and halogen exchange with carboxylate resulted in P-stereogenic compounds in excellent ee (up to >99 %). The isolation of cobaltacycle involved in the catalytic cycle and the outcome of control experiments provide support for a plausible mechanism.

Exploiting the Synergism of a Carbon-Catalyst Interface to Achieve Magneto-Electrocatalytic Overall Water Splitting at 2.197 V.

The desire to electrolyze water at low energy and high kinetics for achieving rapid H2 production forms the holy grail for the paradigm shift to a sustainable H2-driven economy. While alkaline electrolysis is preferred due to the use of earth-abundant catalysts, its sluggish kinetics and high overpotential are the persistent challenges. Addressing this, we demonstrate the coupling of an externally applied magnetic field (Hext) to a synergistically designed interface of nanostructured carbon floret with antiferromagnetic NiO nanoflakes that act in unison to achieve rapid hydrogen generation (6.3 N m3 h-1 W-1) that is comparable with existing technologies. Specifically, the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) overpotentials are simultaneously reduced by 10 and 7%, respectively, under the influence of a weak fridge magnet (Hext = 200 mT). Consequently, ∼11% improvement in the energy efficiency is observed with a 21% reduced cell voltage for overall water splitting. The stability of the system is demonstrated over a prolonged lifetime of ∼95 h. This performance enhancement with Hext for both HER and OER is explained in terms of improved kinetic facility for the reaction and lower resistance of charge transfer pathway. Moreover, the electrocatalyst is seen to retain the improved performance for prolonged usage (∼3 h) even after the removal of the Hext, and hence, it provides an energy-efficient hydrogen and oxygen generation pathway.