Electronic and Magnetic Properties of Infinite 1D Chains of Paddlewheel Carboxylates M₂(COOR)₄ (M = Mo, W, Ru, Rh, Ir, Cu)

Dinuclear complexes of transition metals bridged by four carboxylate-groups are examples of stable atomic configurations serving as fundamental building blocks of catalysts and prototypical molecular electronic devices. The electronic structure and magnetic properties of many molecular tetracarboxylate complexes were meticulously studied; however, the properties of the one-dimensional (1D) polymeric chain of associated tetracarboxylates have so far evaded much attention. Using periodic density-functional theory calculations, we analyze the electronic structure of condensed tetracarboxylates Mo­(II), W­(II), Ru­(II), Rh­(II), Ir­(II), and Cu­(II). The relationship between crystal structure of the polymerized tetracarboxylates and the electronic properties of the metal–metal bond in the M₂⁴⁺ core is studied. The electronic effects emanating from the association of dinuclear transition metal tetracarboxylates are important for designing molecular electronic devices. In this study, its influence on both direct and indirect metal–metal interactions, and the electronic structure, in particular transport properties, is discussed

Bedford-Type Palladacycle-Catalyzed Miyaura Borylation of Aryl Halides with Tetrahydroxydiboron in Water

A mild aqueous protocol for palladium catalyzed Miyaura borylation of aryl iodides, aryl bromides and aryl chlorides with tetrahydroxydiboron (BBA) as a borylating agent is developed. The developed methodology requires low catalyst loading of Bedford-type palladacycle catalyst (0.05 mol %) and works best under mild reaction conditions at 40 °C in short time of 6 h in water. In addition, our studies show that for Miyaura borylation using BBA in aqueous condition, maintaining a neutral reaction pH is very important for reproducibility and higher yields of corresponding borylated products. Moreover, our protocol is applicable for a broad range of aryl halides, corresponding borylated products are obtained in excellent yields up to 93% with 29 examples demonstrating its broad utility and functional group tolerance

Identification and Experimental Characterization of an Extremophilic Brine Pool Alcohol Dehydrogenase from Single Amplified Genomes

Because only 0.01% of prokaryotic genospecies can be cultured and <i>in situ</i> observations are often impracticable, culture-independent methods are required to understand microbial life and harness potential applications of microbes. Here, we report a methodology for the production of proteins with desired functions based on single amplified genomes (SAGs) from unculturable species. We use this method to resurrect an alcohol dehydrogenase (ADH/D1) from an uncharacterized halo-thermophilic archaeon collected from a brine pool at the bottom of the Red Sea. Our crystal structure of 5,6-dihydroxy NADPH-bound ADH/D1 combined with biochemical analyses reveal the molecular features of its halo-thermophily, its unique habitat adaptations, and its possible reaction mechanism for atypical oxygen activation. Our strategy offers a general guide for using SAGs as a source for scientific and industrial investigations of “microbial dark matter.