The design and synthesis of copper complexes that can reduce nitrite to NO has attracted considerable interest. They have been guided by the structural information on the catalytic Cu centre of the widespread enzymes Cu nitrite reductases but the chemically novel side-on binding of NO observed in all crystallographic studies of these enzymes has been questioned in terms of its functional relevance. ...

Nickel norcorrole provides an unusual example of a molecule that is strongly antiaromatic according to the magnetic criterion, but which exhibits, according to high-quality DFT calculations, a symmetric, delocalized structure with no difference in bond length between adjacent C_meso-C_α bonds. A fragment molecular orbital analysis suggests that these discordant observations are ...

Density functional theory calculations with the B3LYP*-D3 method with large STO-QZ4P basis sets unambiguously predict a singlet ground state for Zn-porphyryne. However, the calculations also predict a low singlet–triplet gap of about 0.4 eV and a high adiabatic electron affinity of 2.4 eV. Accordingly, the reactivity of porphyryne species may be dominated by electron transfer, hydrogen abstraction, ...

Relativistic and nonrelativistic density functional theory calculations were used to investigate rare or nonexistent ruthenium and osmium analogues of nitrosylhemes. Strong ligand field effects and, to a lesser degree, relativistic effects were found to destabilize {RuNO}⁷ porphyrins relative to their {FeNO}⁷ analogues. Substantially stronger relativistic effects account for ...

Ruthenium had up to date been pivotal in electro- and photocatalytic applications involving reduction of CO₂ and H₂O, and dye-sensitized solar cells. Commercial applications would seek use of earth-abundant metals instead. Towards this goal, it is key to review the synthesis, electrochemical and spectroscopical properties of associated metal-to-ligand charge transfer complexes ...

The interaction of free-base triarylcorroles with Re₂(CO)₁₀ in 1,2- dichlorobenzene in the presence of 2,6-lutidine at 180 °C under strict anerobic conditions afforded approximately 10% yields of rhenium corrole dimers. The compounds exhibited diamagnetic ¹ H NMR spectra consistent with a metal−metal quadruple bond with a σ² π⁴ δ² ...

A series of novel ferrocenylsubphthalocyanine dyads Y-BSubPc(H)₁₂ with ferrocenylcarboxylic acids Y-H = (FcCH₂CO₂-H), (Fc(CH₂)₃CO₂-H) or (FcCO(CH₂)₂CO₂-H) in the axial position were synthesized from the parent Cl-BSubPc(H)₁₂ via an activated triflate-SubPc intermediate. UV/Vis data revealed ...

xploratory scalar-relativistic density functional theory (B3LYP*-D3/ZORA-STO-TZ2P) calculations have been used to examine the stability and bonding of pseudotetrahedral Group 8 (Fe, Ru, and Os) and Group 9 (Co, Rh, and Ir) terminal carbide complexes with dδ4 ground states and tripodal tris(N-heterocyclic-carbene) supporting ligands. The calculations predict relatively low adiabatic ionization ...

Explicit calculations of vertical and adiabatic ionization potentials of cyclopropane derivatives with modern DFT methods have underscored the possibility of unusually large reorganization energies (defined as the difference between vertical and adiabatic ionization potentials) of 0.5–1.0 eV for several compounds. Such is the case for ionization of the twist-bent σ-bond of trans-bicyclo[4.1.0]hept-3-ene ...