EPR evidence of local lattice mode in K3H(SO4)2 and Rb3H(SO4)2 fast-proton conductors

The observation of an anomalous temperature dependence of Mn²⁺ EPR spectra linewidth and nonaxial crystal-field parameter in K₃H(SO₄)₂ and Rb₃H(SO₄)₂ allows one to suggest the presence of “local mode” predicted by Yamada (Ferroelectrics 170 (1995) 23). The activation energy for this kind of excitation was found and equals 11.3 (0.5) and 7.4 (0.3) meV for Mn²⁺ doped K₃H(SO₄)₂ and Rb₃H(SO₄)₂, respectively.     

Planar Chiral Rhodium Complexes of 1,4-Benzoquinones

Diene rhodium complexes are important catalysts in modern organic synthesis. Herein, we report a new approach to such complexes with the uncommon planar chirality. The synthesis is achieved by face-selective coordination of the prochiral 2,5-disubstituted-1,4-benzoquinones (R₂-Q) with rhodium precursors containing the chiral auxiliary ligand S-salicyl-oxazoline (S-Salox). Such coordination leads to the formation of (R,R-R₂-Q)Rh(S-Salox) complexes in high yields and with exceptional diastereoselectivity (d. r.>20 : 1). Subsequent replacement of the auxiliary ligand provides various benzoquinone rhodium complexes with retention of the planar chirality. Combined theoretical and experimental studies show that due to their electron-withdrawing nature benzoquinones bind metals stronger than the related 1,4-cyclohexadiene, but weaker than other common diene ligands, such as cyclooctadiene.     

Cyclopentadienyl rhodium(III) complexes as catalysts for the insertion of phenyldiazoacetate into E−H bonds

Rhodium(III) complexes catalyze the insertion of carbenoids generated from diazo compounds into E?H bonds (E = B, Si, N, but not C), although less efficiently than classical rhodium(II) carboxylates, despite formally higher oxidation state of the metal.     

Electrochemically Determining Electronic Structure of ZnO Quantum Dots with Different Surface Ligands

The electronic structure of quantum dots (QDs) including band edges and possible trap states is an important physical property for optoelectronic applications. The reliable determination of the energy levels of QDs remains a big challenge. Herein we employ cyclic voltammetry (CV) to determine the energy levels of three types of ZnO QDs with different surface ligands. Coupled with spectroscopic techniques, it is found that the onset potential of the first reductive wave is likely related to the conduction band edges while the first oxidative wave originates from the trap states. The determined specific energy levels in CV further demonstrates that the ZnO QDs without surface ligands mainly have oxygen interstitial defects whilst the ZnO QDs covered with ligands contain oxygen vacancies. The present electrochemical method offers a powerful and effective way to determine the energy levels of wide bandgap ZnO QDs, which will boost their device performance.     

Postsynthetic Metal and Ligand Exchange in MFU‐4l: A Screening Approach toward Functional Metal–Organic Frameworks Comprising Single‐Site Active Centers

The isomorphous partial substitution of Zn²⁺ ions in the secondary building unit (SBU) of MFU‐4l leads to frameworks with the general formula [M_xZn_(5–x)Cl₄(BTDD)₃], in which x≈2, M=Mn^II, Fe^II, Co^II, Ni^II, or Cu^II, and BTDD=bis(1,2,3‐triazolato‐[4,5‐b],[4′,5′‐i])dibenzo‐[1,4]‐dioxin. Subsequent exchange of chloride ligands by nitrite, nitrate, triflate, azide, isocyanate, formate, acetate, or fluoride leads to a variety of MFU‐4l derivatives, which have been characterized by using XRPD, EDX, IR, UV/Vis‐NIR, TGA, and gas sorption measurements. Several MFU‐4l derivatives show high catalytic activity in a liquid‐phase oxidation of ethylbenzene to acetophenone with air under mild conditions, among which Co‐ and Cu derivatives with chloride side‐ligands are the most active catalysts. Upon thermal treatment, several side‐ligands can be transformed selectively into reactive intermediates without destroying the framework. Thus, at 300 °C, Co^II‐azide units in the SBU of Co‐MFU‐4l are converted into Co^II‐isocyanate under continuous CO gas flow, involving the formation of a nitrene intermediate. The reaction of Cu^II‐fluoride units with H₂ at 240 °C leads to Cu^I and proceeds through the heterolytic cleavage of the H₂ molecule.     

Enantioselective C−H Activation with Earth‐Abundant 3d Transition Metals

Molecular syntheses largely rely on time‐ and labour‐intensive prefunctionalization strategies. In contrast, C?H activation represents an increasingly powerful approach that avoids lengthy syntheses of prefunctionalized substrates, with great potential for drug discovery, the pharmaceutical industry, material sciences, and crop protection, among others. The enantioselective functionalization of omnipresent C?H bonds has emerged as a transformative tool for the step‐ and atom‐economical generation of chiral molecular complexity. However, this rapidly growing research area remains dominated by noble transition metals, prominently featuring toxic palladium, iridium and rhodium catalysts. Indeed, despite significant achievements, the use of inexpensive and sustainable 3d metals in asymmetric C?H activations is still clearly in its infancy. Herein, we discuss the remarkable recent progress in enantioselective transformations via organometallic C?H activation by 3d base metals up to April 2019.     

“(Diphosphine)Nickel”‐Catalyzed Negishi Cross‐Coupling: An Experimental and Theoretical Study

The use of a strongly donating “(bis‐dialkylphosphine)Ni” fragment promotes the catalytic coupling of a large range of ArCl and ArZnCl derivatives under mild conditions. Stoichiometric mechanistic investigations and DFT calculations prove that a Ni⁰/Ni^II cycle is operative in this system.     

Topological and Steric Constraints to Stabilize Heteroleptic Copper(I) Complexes Combining Phenanthroline Ligands and Phosphines

Heteroleptic copper(I) complexes combining phenanthroline derivatives (NN) and chelating bisphosphine ligands (PP) are an important class of luminescent materials for various applications. Although thermodynamically stable, [Cu(NN)(PP)]⁺ derivatives are also kinetically unstable. As a result, a dynamic ligand-exchange reaction is often observed in solution, leading to a dynamic mixture of heteroleptic and homoleptic complexes. To prevent the formation of the homoleptic species, macrocyclic phenanthroline ligands have been used for the preparation of [Cu(NN)(PP)]⁺ pseudorotaxanes. The topological constraint resulting from the macrocyclic structure of the NN ligand drives the thermodynamic equilibrium towards the exclusive formation of the heteroleptic complex as long as the macrocycle is large and flexible enough to allow for the threading of the PP ligand. Conversely, when the threading is prevented by steric constraints, unprecedented copper(I) complexes with a trigonal coordination geometry are obtained. These results are summarized in the present concept article.     

Chiral Ligands in Hypervalent Iodine Compounds: Synthesis and Structures of Binaphthyl-Based λ3-Iodanes

Several novel binaphthyl-based chiral hypervalent iodine(III) reagents have been prepared and structurally analysed. Various asymmetric oxidative reactions were applied to evaluate the reactivities and stereoselectivities of those reagents. Moderate to excellent yields were observed; however, very low stereoselectivities were obtained. NMR experiments indicated that these reagents are very easily hydrolysed in either chloroform or DMSO solvents leading to the limited stereoselectivities. It is concluded that the use of chiral ligands is an unsuccessful way to prepare efficient stereoselective iodine(III) reagents.