Molecular oxofluorides OMFn of nickel, palladium and platinum: oxyl radicals with moderate ligand field inversion

High-valent late transition metal oxo compounds attracted attention because of their peculiar metal–oxygen bond. Their oxo ligands exhibit an electrophilic and distinct radical oxyl (O˙−) rather than the more common nucleophilic (O2−) character.

Destruction and reconstruction of UO22+ using gas-phase reactions

While the strong axial U=O bonds confer high stability and inertness to UO22+, it has been shown that the axial oxo ligands can be eliminated or replaced in the gas-phase...

Probing the Electronic Structure of Spectator Oxo Ligands by 17O NMR Spectroscopy

Spectator oxo ligands are ubiquitous in catalysis, in particular in olefin epoxidation and olefin metathesis. Here we use computationally derived 17O NMR parameters to probe the electronic structure of spectator oxo ligands in these two reactions. We show that 17O NMR parameters allow to distinguish between doubly-bonded and triply-bonded oxo ligands, giving detailed insights into the frontier molecular orbitals involved in the metaloxo bonds along the reaction pathway. On the one hand, our study shows that in olefin epoxidation catalysed by methyltrioxorhenium (MTO), the oxo ligand significantly changes its bonding mode upon formation of the oxygen-transferring Re-oxo-bisperoxo-species, changing its nature from a doubly bonded to a triply bonded oxo ligand. On the other hand, only minor changes in the binding mode are found along the olefin metathesis reaction pathway with Mo- and W-based oxo-alkylidene species, in which the oxo ligand behaves as a triply bonded ligand throughout the reaction. This finding contrasts earlier studies that proposed that the change of binding mode of the oxo ligand was key to metallacyclobutane formation.

M(VI) Oxidation State Stabilization in Iron, Cobalt and Nickel Heteroligand Metal Chelates Containing 3,7,11,15-Tetraazaporphine and Two Axial Oxo Ligands: Quantum-Chemical Simulation

The quantum-chemical calculation of iron, cobalt and nickel heteroligand complexes with the double deprotonated form of (NNNN)-donor atomic ligand—3,7,11,15-tetraazaporphine—and two oxo ligands has been carried out. Data on the structural and standard thermodynamic parameters, NBO analysis and multiplicity of the ground states of these complexes have been presented. The given calculation has been made by using the density functional theory (DFT) method with the OPBE/TZVP basis set. Based on the results of this calculation, the possibility of the existence of oxidation state VI for the chemical elements indicated above—unusual for iron and cobalt, and for nickel, unknown at all—has been shown.

Cobalt-bridged secondary building units in a titanium metal–organic framework catalyze cascade reduction of N-heteroarenes

We report here the synthesis of a robust Ti–MOF with novel SBUs and its use as oxo ligands to chelate Co-hydrides for cascade reduction of N-heteroarenes.