The nature of Cu bonding to natural organic matter

We present a fully flexible and ab initio-derived molecular mechanics force field for the ubiquitous copper paddle-wheel building block Cu2(O2C)4 in metal−organic frameworks. The force field expression is based on the established MM3 force field, extended by additional cross terms and specific bond-stretching and angle-bending terms for the square-planar CuO4 coordination environment. Using reference data computed at the DFT level for nonperiodic reference systems, the parametrization is performed using an automated genetic algorithm optimization strategy in order to reproduce structure and low normal modes of the model systems. It is validated on the much investigated Cu-btc (HKUST-1) metal−organic framework. Beyond the structure, lattice-dynamic-dependent properties such as the bulk modulus and the observed negative thermal expansion effect of Cu-btc are quantitatively predicted by the force field without recourse with respect to experimental data. In connection with available parametrizations of variou...

First-Principles-Derived Force Field for Copper Paddle-Wheel-Based Metal−Organic Frameworks

Crystal structures and spectroscopic behavior of monomeric, dimeric and polymeric copper(II) chloroacetate adducts with isonicotinamide, N-methylnicotinamide and N,N-diethylnicotinamide

Research on O2 activation at ligated Cu(I) is fueled by its biological relevance and the quest for efficient oxidation catalysts. A rarely observed reaction is the formation of a Cu(II) -O-Cu(II) species, which is more special than it appears at first sight: a single oxo ligand between two Cu(II) centers experiences considerable electron density, and this makes the corresponding complexes reactive and difficult to access. Hence, only a small number of these compounds have been synthesized and characterized unequivocally to date, and as biological relevance was not apparent, they remained unappreciated. However, recently they moved into the spotlight, when Cu(II) -O-Cu(II) cores were proposed as the active species in the challenging oxidation of methane to methanol at the surface of a Cu-grafted zeolite and in the active center of the copper enzyme particulate methane monooxygenase. This Minireview provides an overview of these systems with a special focus on their reactivity and spectroscopic features.

Molecular Cu(II)-O-Cu(II) complexes: still waters run deep.

Ferromagnetic trinuclear carbonato-bridged and tetranuclear hydroxo-bridged Cu(II) compounds with 4,4′-dimethyl-2,2′-bipyridine as ligand. X-ray structure, spectroscopy and magnetism

This review summarizes the data for over nine hundred dimeric Cu(II) coordination compounds. There are several types of the bridges, from which doubly bridges by far prevail. The most common ligands are O− and N− donors. From the stereochemical point of view, a square-pyramidal arrangement with different degrees of distortion about Cu(II), is the most common. Several relationships were found between the Cu-Cu distances and the Cu-L-Cu bridge angle and the type of bridging, between the intra-ligand L-Cu-L ring angles and coordination numbers.

Ľubov Macåškovå

Papers

Copper(ii) coordination compounds: classification and analysis of crystallographic and structural data iii. dimeric compounds