How Ligand Geometry Affects the Reactivity of Co(II) Cyclam Complexes

Cobalt complexes are extensively studied as bioinspired models for non-heme oxygenases as they facilitate both the stabilization and characterization of metal-oxygen intermediates. As an analog to the well-known Co(cyclam) complex Co{N₄} (cyclam=1,4,8,11-tetraazacyclotetradecane), the Co^II complex Co{i-N₄} with the isomeric isocyclam ligand (isocyclam=1,4,7,11-tetraazacyclotetradecane) was synthesized and characterized. Despite the identical N₄ donor set of both complexes, Co{i-N₄} enables the 2e⁻/2H⁺ reduction of O₂ with a lower overpotential (η_eff of 385 mV vs. 540 mV for Co{N₄} ), albeit with a diminished turnover frequency. Characterization of the intermediates formed upon O₂ activation of Co{i-N₄} reveals a structurally identified stable μ-peroxo Co^III dimer as the main product. A superoxo Co^III species is also formed as a minor product, as indicated by EPR spectroscopy. In further reactivity studies, the electrophilicity of these in situ generated Co−O₂ species was demonstrated by the oxidation of the O−H bond of TEMPO−H (2,2,6,6-tetramethylpiperidin-1-ol) via a H atom abstraction process. Unlike the known Co(cyclam), Co{i-N₄} can be employed in oxygen atom transfer reactions oxidizing triphenylphosphine to the corresponding phosphine oxide highlighting the impact of geometrical modifications of the ligand while preserving the ring size and donor atom set on the reactivity of biomimetic oxygen activating complexes.     

Electrochemical CO2 and Proton Reduction by a Co(dithiacyclam) Complex

While [Ni(cyclam)]²⁺ and [Ni(dithiacyclam)]²⁺ complexes were shown to be potent electrocatalysts for the CO₂ conversion, their respective Co complexes hitherto received only little attention. Herein, we report on the Co^II complexes of the cyclam and dithiacyclam platform, describe their synthesis and reveal their rich solvent dependent coordination chemistry. We show that sulfur implementation into the cyclam moiety leads to a switch from a low spin Co^II complex in [Co(cyclam)]²⁺ to a high spin form in [Co(dithiacyclam)]²⁺. Notably, while both complexes are capable to perform the reduction of CO₂ to CO, H₂ formation is generally preferred. Along this line, the complexes were shown to enable proton reduction from acetic acid. However, in comparison to [Co(cyclam)]²⁺, the altered electronics make [Co(dithiacyclam)]²⁺ complexes prone to deposit on the glassy carbon working electrode over time leading to an overall low faradaic efficiency for the reduction of protons or CO₂.     

Acoustic cavitation inception

This article presents a selective review of the subject of acoustic cavitation inception. Topics covered include cavitation threshold measurements, the role of dirt or pre-existing bubble nuclei in cavitation inception, radiation-induced acoustic cavitation, and a discussion of some unsolved problems such as cavitation thresholds in liquid helium and the effects of electric fields on thresholds.     

Acoustic microcavitation: its active and passive acoustic detection

In this work acoustic microcavitation in water is studied primarily at 0.75 MHz and 1% duty cycle. To detect cavitation, two kinds of acoustic detectors are used. The first one is an unfocused, untuned 1-MHz receiver transducer that serves as a passive detector. The other one is a focused 30-MHz transducer that is used in pulse-echo mode and is called the active detector. Cavitation itself is brought about by a focused PZT-8 crystal driven in pulse mode. The active detector is arranged confocally with respect to the cavitation transducer. Both the interrogating pulse and the cavitation pulse arrive simultaneously at the common focus, which is the region of cavitation. With the test chamber filled with clean water, no cavitation is observed, even when the cavitation transducer is driven to give its peak output of 22 bar peak negative. Cavitation is, however, observed when polystyrene microparticles are added to the host water. Our view of how these smooth, spherical, monodispersed microparticles give rise to cavitation is described with some estimates. An attempt has been made to understand whether the presence of "streaming" affects the thresholds, and it has been found that the active detector field affects the cavitation process.     

Acoustic microcavitation: enhancement and applications

Experimental investigation into acoustic microcavitation is extended to include "cavitation activity" in addition to the threshold measurements using acoustic detectors. The primary setup incorporates two detectors: an unfocused, untuned 1-MHz transducer, which serves as a passive detector, and a focused 30-MHz transducer used in pulse-echo mode as the active detector. Cavitation itself is brought about by a focused piezoelectric transducer driven in pulse mode. The active detector is arranged confocally with respect to the cavitation transducer. Both the interrogating pulse and the cavitation pulse arrive simultaneously at the common focus which is the region of cavitation. Cavitation is conducted primarily at 0.75 MHz and 1% duty cycle in clean water using microparticles to seed the events. Cavitation activity appears to be directly proportional to the number density of the particles present in the cavitation medium. The fact that the active detector affects the cavitation process can be further exploited to seek interesting applications leading possibly to submicronic particle counting and testing of surface characteristics of silica particles used in liquid chromatography.     

Heteronukleare Komplexverbindungen mit Metall—Metall-Bindungen. IX [1]. Amin-kupfer(I)-carbonylmetallate mit Cobalt,Eisen oder Mangan

Heteronuclear Coordination Compounds with Metal—Metal Bonds. IX. Amine Copper(I) Carbonyl Metalates with Cobalt, Iron, or Manganese Colourless crystals of the carbonyl copper complex [(NH₃)₃(CO)Cu][Co(CO)₄] ( 1 a ) are formed in the reaction of [Cu(NH₃)₄]Cl and Na[Co(CO)₄] (T < ? 8°C, p_CO = 1 bar); above ?5°C and under N₂-atmosphere 1 a converts to [(NH₃)₂CuCo(CO)₄] ( C ), which serves as a starting material for the synthesis of new copper cobaltates: the amines N-amino piperidine, N,N-dimethyl ethylenediamine (dmed) and N-benzyl N,N′-dimethyl ethylenediamine (bn-dmed) replace NH₃ to form [(C₅H₁₀N? NH₂)₃CuCo(CO)₄] ( 1 b ), [(dmed)CuCo(CO)₄] ( 1 c ), [(bn-dmed)CuCo(CO)₄] ( 1 d ) the Cu? Co-bond remaining intact. [(NH₃)₂CuFe(CO)₃NO] ( 2 a ) is isosteric with C ; it is synthesized from [Cu(NH₃)₄]Cl and Na[Fe(CO)₃NO] in aqueous solution; 2 a reacts with N,N,N′,N′-tetramethyl ethylenediamine (tmed) to form [(tmed)(NH₃)CuFe(CO)₃NO] ( 2b ). The [Mn(CO)₅]^? ion reacts with ammine copper ions to form the tetranuclear cluster [{(NH₃)CuMn(CO)₅}₂] ( 3 ). All new compounds have been investigated by X-ray structure analysis.     

A turbidity study of particle interaction in latex suspensions

A turbidimetric analysis of particle interaction in latex suspensions is given. The turbidity measured at different wavelengths can be rendered by the product of an integrated form factorQ(²) and a suitably defined integrated structure factorZ(²,c). This factorization rests on the expansion of the form factor of the particlesP(q) and the structure factorS(q) [q=(4/)sin(/2); : scattering angle] of the system in even powers ofq. The accuracy of this approximation has been shown by calculating the turbidity for a system of hard spheres in terms of the Percus-Yevick structure factor by numerical integration. Also, the effect of polydispersity has been taken into account within the frame of Percus-Yevick-Vrij theory for non-uniform hard spheres. It is shown that the influence of small polydispersity (standard deviation below 8%) is within experimental uncertainty. The method is applied to precise UV-spectra (400800 nm) obtained from a polystyrene latex with a diameter of 77.4 nm. The integrated structure factorZ(²,c) obtained experimentally can be interpreted in terms of an effective diameter of interaction giving a measure for the strength of electrostatic interaction.     

Synthesis and Electrochemical Investigation of Phosphine Substituted Diiron Phosphadithiolate Complexes

This work reports on ligand exchange reactions between a [FeFe] hydrogenase model containing the higher homologue ( PhosDT ) and phosphines selected to cover a variety of electronic properties and possible coordination modes. Additionally, the amount of the phosphines and the reaction temperature were varied to study the formation of complexes with multiple phosphines or altered binding modes. Due to steric effects caused by the position of the bridgehead, the phosphines bind preferentially at the more accessible iron centre on the phosphinate averted side. While all ligand exchanges resulted in a ligand-specific main product at room temperature, reflux conditions induced decomposition in case of PhosDT-(κ²-dppe) and PhosDT-(κ²-dppv) and a change in the binding mode for the dppm containing complex. Moreover, we highlight two novel iron complexes obtained as side products of the reactions with dppe and dppv, while in case of dppm an additional model with two bridging phosphine ligands was generated. Finally, the six novel phosphine substituted PhosDT models were electrochemically investigated, revealing a cathodic shift compared to the starting material due to the increased electron density at the iron atoms. Moreover, the models with monodentate ligands exhibit a different CV pattern for the Fe^IFe^I/Fe^IFe⁰ process than complexes with bidentate phosphines.