A Multistep Oxidative Cascade Reaction from a Naphthalenediol-Based Pre-Ligand to a Tetranuclear Perylenequinone-Based Fe Complex.

We have developed a family of dinuclear complexes using 2,7-disubstituted 1,8-naphthalenediol ligands that bind by molecular recognition to two neighboring phosphate diesters of the DNA backbone with the dinuclear Cu and Ni complexes exhibiting a severe cytotoxicity for human cancer cells. To increase the binding affinity, we intended to synthesize the corresponding dinuclear Fe complex. Surprisingly, we obtained a tetranuclear Fe perylene-based complex instead of the expected dinuclear Fe naphthalene-based complex.

Surviving a classic heat stroke/hyperthermia > 42 °C - a case report.

Introduction: Classic heat stroke is a severe trauma which can lead to multi-organ dysfunctions and is associated with a high mortality.

Case Presentation: In this case report we present a 73-year-old patient with a classic heat stroke. His initial core body temperature was over 42 °C and he had a GCS of 3.

Increasing the electron donation in a dinucleating ligand family: molecular and electronic structures in a series of CoCo complexes.

We have developed a family of dinucleating ligands with varying terminal donors to generate dinuclear peroxo and high-valent complexes and to correlate their stabilities and reactivities with their molecular and electronic structures as a function of the terminal donors. It appears that the electron-donating ability of the terminal donors is an important handle for controlling these stabilities and reactivities. Here, we present the synthesis of a new dinucleating ligand with potentially strong donating terminal imidazole donors.

Generation and Reactivity of μ-1,2-Peroxo CuCu and Bis-μ-oxo CuCu Species and Catalytic Hydroxylation of Benzene to Phenol with Hydrogen Peroxide.

Tetradentate-N ligands stabilize dinuclear {Cu(μ-1,2-peroxo)Cu} and {Cu(μ-O)Cu} species, and Cu complexes of these ligands were reported to catalyze the oxidation of benzene with HO. Here, we report {Cu(μ-1,2-peroxo)Cu} and {Cu(μ-O)Cu} intermediates of dinucleating bis(tetradentate-N) ligands depending on the absence or presence of 6-methyl substituents on the terminal pyridine donors, respectively, generated either from {CuCu} precursors with O or from {CuCu} precursors with HO and NEt. Both intermediates are not stable even at low temperatures, but they show no electrophilic HAT reactivity with DHA.

Direct and remote control of electronic structures and redox potentials in μ-oxo diferric complexes.

Non-heme diiron enzymes activate O for the oxidation of substrates in the form of peroxo FeIII2 or high-valent FeIV2 intermediates. We have developed a dinucleating bis(tetradentate) ligand system that stabilizes peroxo and hydroperoxo FeIII2 complexes with terminal 6-methylpyridine donors, while the peroxo FeIII2 intermediate is reactive with terminal pyridine donors presumably conversion to a fluent high-valent FeIV2 intermediate. We present here a derivative with electron-donating methoxy substituents at the pyridine donors and its diferric complexes with an {FeX(μ-O)FeX} (X = Cl, OAc, and OH) or an {Fe(μ-O)(μ-OAc)Fe} core.