Light-Driven Hydrodefluorination of Electron-Rich Aryl Fluorides by an Anionic Rhodium-Gallium Photoredox Catalyst.

An anionic Rh-Ga complex catalyzed the hydrodefluorination of challenging C-F bonds in electron-rich aryl fluorides and trifluoromethylarenes when irradiated with violet light in the presence of H , a stoichiometric alkoxide base, and a crown-ether additive. Based on theoretical calculations, the lowest unoccupied molecular orbital (LUMO), which is delocalized across both the Rh and Ga atoms, becomes singly occupied upon excitation, thereby poising the Rh-Ga complex for photoinduced single-electron transfer (SET). Stoichiometric and control reactions support that the C-F activation is mediated by the excited anionic Rh-Ga complex.

One-electron bonds in copper-aluminum and copper-gallium complexes.

Odd-electron bonds have unique electronic structures and are often encountered as transiently stable, homonuclear species. In this study, a pair of copper complexes supported by Group 13 metalloligands, M[N((-CH)NCHPPr)] (M = Al or Ga), featuring two-center/one-electron (2c/1e) σ-bonds were synthesized by one-electron reduction of the corresponding Cu(i) ⇢ M(III) counterparts. The copper bimetallic complexes were investigated by X-ray diffraction, cyclic voltammetry, electron paramagnetic spectroscopy, and density functional theory calculations.

Bimetallic iron-tin catalyst for N to NH and a silyldiazenido model intermediate.

A tin-supported iron catalyst produces 5.9 turnovers of NH3 from N2, using [Ph2NH2]OTf as the acid and CoCp2* as the reductant. Two redox states of the Fe(N2) adduct and an Fe silyldiazenido complex were characterized using X-ray crystallography along with NMR and Mössbauer spectroscopies.

Spatial Distribution of Soil Phosphorus, Calcium, and pH after Long-term Broiler Litter Application.

Water movement over and through soil is largely driven by topography and soil management across landscapes. This research tested the hypothesis that the water movement determines the potential for P and Ca redistribution and pH variance across landscapes. This hypothesis was evaluated by using digital elevation model-derived terrain attributes in fields after 55 yr of broiler litter applications on pastures in Smith County, Mississippi.