Catalytic Light-Driven Generation of Hydrogen from Water by Iron Dithiolene Complexes

The development of active, robust systems for light-driven hydrogen production from aqueous protons based on catalysts and light absorbers composed solely of earth abundant elements remains a challenge in the development of an artificial photosynthetic system for water splitting. Herein, we report the synthesis and characterization of four closely related Fe bis­(benzenedithiolate) complexes that exhibit catalytic activity for hydrogen evolution when employed in systems with water-soluble CdSe QDs as photosensitizer and ascorbic acid as a sacrificial electron source under visible light irradiation (520 nm). The complex with the most electron-donating dithiolene ligand exhibits the highest activity, the overall order of activity correlating with the reduction potential of the formally Fe­(III) dimeric dianions. Detailed studies of the effect of different capping agents and the extent of surface coverage of these capping agents on the CdSe QD surfaces reveal that they affect system activity and provide insight into the continued development of such systems containing QD light absorbers and molecular catalysts for H₂ formation

Catalytic Light-Driven Generation of Hydrogen from Water by Iron Dithiolene Complexes

The development of active, robust systems for light-driven hydrogen production from aqueous protons based on catalysts and light absorbers composed solely of earth abundant elements remains a challenge in the development of an artificial photosynthetic system for water splitting. Herein, we report the synthesis and characterization of four closely related Fe bis­(benzenedithiolate) complexes that exhibit catalytic activity for hydrogen evolution when employed in systems with water-soluble CdSe QDs as photosensitizer and ascorbic acid as a sacrificial electron source under visible light irradiation (520 nm). The complex with the most electron-donating dithiolene ligand exhibits the highest activity, the overall order of activity correlating with the reduction potential of the formally Fe­(III) dimeric dianions. Detailed studies of the effect of different capping agents and the extent of surface coverage of these capping agents on the CdSe QD surfaces reveal that they affect system activity and provide insight into the continued development of such systems containing QD light absorbers and molecular catalysts for H₂ formation

Electronic Structure and Bonding in Iron(II) and Iron(I) Complexes Bearing Bisphosphine Ligands of Relevance to Iron-Catalyzed C–C Cross-Coupling

Chelating phosphines are effective additives and supporting ligands for a wide array of iron-catalyzed cross-coupling reactions. While recent studies have begun to unravel the nature of the in situ-formed iron species in several of these reactions, including the identification of the active iron species, insight into the origin of the differential effectiveness of bisphosphine ligands in catalysis as a function of their backbone and peripheral steric structures remains elusive. Herein, we report a spectroscopic and computational investigation of well-defined FeCl₂(bisphosphine) complexes (bisphosphine = SciOPP, dpbz, ^tBudppe, or Xantphos) and known iron­(I) variants to systematically discern the relative effects of bisphosphine backbone character and steric substitution on the overall electronic structure and bonding within their iron complexes across oxidation states implicated to be relevant in catalysis. Magnetic circular dichroism (MCD) and density functional theory (DFT) studies demonstrate that common <i>o</i>-phenylene and saturated ethyl backbone motifs result in small but non-negligible perturbations to 10<i>Dq</i>(<i>T</i>_<i>d</i>) and iron–bisphosphine bonding character at the iron­(II) level within isostructural tetrahedra as well as in five-coordinate iron­(I) complexes FeCl­(dpbz)₂ and FeCl­(dppe)₂. Notably, coordination of Xantphos to FeCl₂ results in a ligand field significantly reduced relative to those of its iron­(II) partners, where a large bite angle and consequent reduced iron–phosphorus Mayer bond orders (MBOs) could play a role in fostering the unique ability of Xantphos to be an effective additive in Kumada and Suzuki–Miyaura alkyl–alkyl cross-couplings. Furthermore, it has been found that the peripheral steric bulk of the SciOPP ligand does little to perturb the electronic structure of FeCl₂(SciOPP) relative to that of the analogous FeCl₂(dpbz) complex, potentially suggesting that differences in the steric properties of these ligands might be more important in determining in situ iron speciation and reactivity

A Pseudotetrahedral Uranium(V) Complex

A series of uranium amides were synthesized from <i>N</i>,<i>N</i>,<i>N</i>-cyclohexyl­(trimethylsilyl)lithium amide [Li]­[N­(TMS)­Cy] and uranium tetrachloride to give U­(NCySiMe₃)_<i>x</i>(Cl)_4–<i>x</i>, where <i>x</i> = 2, 3, or 4. The diamide was isolated as a bimetallic, bridging lithium chloride adduct ((UCl₂(NCyTMS)₂)₂-LiCl­(THF)₂), and the tris­(amide) was isolated as the lithium chloride adduct of the monometallic species (UCl­(NCyTMS)₃-LiCl­(THF)₂). The tetraamide complex was isolated as the four-coordinate pseudotetrahedron. Cyclic voltammetry revealed an easily accessible reversible oxidation wave, and upon chemical oxidation, the U^V amido cation was isolated in near-quantitative yields. The synthesis of this family of compounds allows a direct comparison of the electronic structure and properties of isostructural U^IV and U^V tetraamide complexes. Spectroscopic investigations consisting of UV–vis, NIR, MCD, EPR, and U L₃-edge XANES, along with density functional and wave function calculations, of the four-coordinate U^IV and U^V complexes have been used to understand the electronic structure of these pseudotetrahedral complexes