Chalcogenido-Dimethylgallates and -Indates DMPyr [Me M(μ -E)] (M=Ga, In; E=S, Se): Building Blocks for Higher and Lower Order Chalcogenidoindates.

Metalation of the anions in the ionic liquids DMPyr[SH] and DMPyr[SeH] (DMPyr=1,1-dimethylpyrrolidinium) by trimethylgallium and trimethylindium is investigated. The reaction proceeds via pre-coordination of [EH] , methane elimination and formation of an unprecedented series of chalcogenido metalates DMPyr [Me M(μ -E)] (M=Ga, In; E=S, Se). These show the presences of dinuclear dianions with four-membered ring structures displaying highly nucleophilic bridging chalcogenide ligands in their crystallographically determined molecular structures.

Allenes for Versatile Iron-Catalyzed C-H Activation by Weak O-Coordination: Mechanistic Insights by Kinetics, Intermediate Isolation, and Computation.

The iron-catalyzed hydroarylation of allenes was accomplished by weak phenone assistance. The C-H activation proceeded with excellent efficacy and high -regioselectivity in proximity to the weakly coordinating carbonyl group for a range of substituted phenones and allenes. Detailed mechanistic studies, including the isolation of key intermediates, the structural characterization of an iron-metallacycle, and kinetic analysis, allowed the sound elucidation of a plausible catalytic working mode.

3d metallaelectrocatalysis for resource economical syntheses.

Resource economy constitutes one of the key challenges for researchers and practitioners in academia and industries, in terms of rising demand for sustainable and green synthetic methodology. To achieve ideal levels of resource economy in molecular syntheses, novel avenues are required, which include, but are not limited to the use of naturally abundant, renewable feedstocks, solvents, metal catalysts, energy, and redox reagents. In this context, electrosyntheses create the unique possibility to replace stoichiometric amounts of oxidizing or reducing reagents as well as electron transfer events by electric current.

Cobaltaelectro-catalyzed C-H activation for resource-economical molecular syntheses.

The direct cleavage of otherwise inert C-H bonds has emerged as a sustainable approach for organic synthesis; in contrast to other approaches, these reactions result in the formation of fewer undesired by-products and do not require pre-functionalization steps. In recent years, oxidative C-H/N-H alkyne annulations and C-H oxygenations were realized by 3d metals. Unfortunately, most of these reactions require stoichiometric amounts of often toxic chemical oxidants.

Azaruthena(II)-bicyclo[3.2.0]heptadiene: Key Intermediate for Ruthenaelectro(II/III/I)-catalyzed Alkyne Annulations.

A ruthenium-catalyzed electrochemical dehydrogenative annulation reaction of imidazoles with alkynes has been established, enabling the preparation of various bridgehead N-fused [5,6]-bicyclic heteroarenes through regioselective electrochemical C-H/N-H annulation without chemical metal oxidants. Novel azaruthenabicyclo[3.2.

Electrophotocatalytic Undirected C-H Trifluoromethylations of (Het)Arenes.

Electrophotochemistry has enabled arene C-H trifluoromethylation with the Langlois reagent CF SO Na under mild reaction conditions. The merger of electrosynthesis and photoredox catalysis provided a chemical oxidant-free approach for the generation of the CF radical. The electrophotochemistry was carried out in an operationally simple manner, setting the stage for challenging C-H trifluoromethylations of unactivated arenes and heteroarenes.

Electrochemical Access to Aza-Polycyclic Aromatic Hydrocarbons: Rhoda-Electrocatalyzed Domino Alkyne Annulations.

Nitrogen-doped polycyclic aromatic hydrocarbons (aza-PAHs) have found broad applications in material sciences. Herein, a modular electrochemical synthesis of aza-PAHs was developed via a rhodium-catalyzed cascade C-H activation and alkyne annulation. A multifunctional O-methylamidoxime enabled the high chemo- and regioselectivity.

Flow Rhodaelectro-Catalyzed Alkyne Annulations by Versatile C-H Activation: Mechanistic Support for Rhodium(III/IV).

A flow-metallaelectro-catalyzed C-H activation was realized in terms of robust rhodaelectro-catalyzed alkyne annulations. To this end, a modular electro-flow cell with a porous graphite felt anode was designed to ensure efficient turnover. Thereby, a variety of C-H/N-H functionalizations proved amenable for alkyne annulations with high levels of regioselectivity and functional group tolerance, viable in both an inter- or intramolecular manner.

Rhodaelectrocatalysis for Annulative C-H Activation: Polycyclic Aromatic Hydrocarbons through Versatile Double Electrocatalysis.

Rapid access to structurally diversified polycyclic aromatic hydrocarbons (PAHs) in a controlled manner is of key significance in materials sciences. Herein, we describe a strategy featuring two distinct electrocatalytic C-H transformations for the synthesis of novel nonplanar PAHs. The combination of rhodaelectrooxidative C-H activation/[2+2+2] alkyne annulation of easily accessible boronic acids with electrocatalytic cyclodehydrogenation provided modular access to diversely substituted PAHs with electricity as a sustainable oxidant.

A Phosphorus Bisylide: Exploring a New Class of Superbases with Two Interacting Carbon Atoms as Basicity Centers.

Herein we present the first superbase MHPN with two interacting P-ylide entities. Unlike classical proton sponges, this novel compound class has carbon atoms as basicity centers which are forced into close proximity by a naphthalene scaffold. The bisylide exhibits an experimental pK  value of 33.

New lithium borates with bistetrazolato and pyrazinediolato ligands - potentially interesting lithium electrolyte additives.

We present a convenient synthesis of the first silylated bistetrazole via a catalyzed twin [2 + 3] cycloaddition of TMS-azide at cyanogen and its application to access bistetrazolatoborates, structurally characterized by a unique unsaturated ten-membered BNC heterocyclic system. Furthermore, new borate anions with two pyrazine-2,3-diolato ligands were synthesized from tetrafluoroborate salts and structurally characterized. Their organic cation can be exchanged for Livia cation exchange.

Simple access to ionic liquids and organic salts containing the phosphaethynolate (PCO(-)) and Zintl (Sb11(3-)) anions.

Herein we report the synthesis of the first ionic liquids with the highly reactive and synthetically valuable phosphaethynolate (PCO(-)) anion. They are simply synthesised by the reaction of organic methylcarbonate salts with P(SiMe3)3. The products are obtained in near to quantitative yields and they are highly viscous liquids at room temperature or have low melting points for symmetric cations.

Mercurates from a Revised Ionothermal Synthesis Route: The Pseudo-Flux Approach.

K2Hg6Se7, Na2Hg3S2.51Se1.49, K2Hg3S1.

Halide-Free Synthesis of Hydrochalcogenide Ionic Liquids of the Type [Cation][HE] (E=S, Se, Te).

We present the synthesis and thorough characterization of ionic liquids and organic salts based on hydrochalcogenide HE(-) (E=S, Se, Te) anions. Our approach is based on halide-, metal-, and water-free decarboxylation of methylcarbonate precursors under acidic conditions, resulting from the easily dissociating reagents H2 E. The compounds were characterized by elemental analysis, multinuclear NMR spectroscopy, thermal and single-crystal XRD analyses.

A new class of deep-blue emitting Cu(I) compounds--effects of counter ions on the emission behavior.

Three deep blue emitting Cu(I) compounds, [Cu(PPh3)tpym]PF6, [Cu(PPh3)tpym]BF4, and [Cu(PPh3)tpym]BPh4 (tpym = tris(2-pyridyl)methane, PPh3 = triphenylphosphine) featuring the tripodally coordinating tpym and the monodentate PPh3 ligands were studied with regard to their structural and photophysical properties. The compounds only differ in their respective counter ions which have a strong impact on the emission properties of the powder samples. For example, the emission quantum yield can be significantly increased for the neat material from less than 10% to more than 40% by exchanging BPh4(-) with PF6(-).

Synthesis of organic (trimethylsilyl)chalcogenolate salts Cat[TMS-E] (E = S, Se, Te): the methylcarbonate anion as a desilylating agent.

A high-yield synthesis of the class of (trimethylsilyl)chalcogenolate organic salts [Cat][TMS-E] (E = S, Se, Te; Cat = BMPyr, DMPyr, NMe4, nBu3MeP) is presented. The title compounds have been prepared by the strictly aprotic reaction between the respective bis(trimethylsilyl)chalcogenide (TMS2E) and methylcarbonate ionic liquids (ILs). This constitutes a novel reaction behavior of methylcarbonate ILs, acting as a nucleophilic desilylating agent and a Lewis base instead of as a Brønsted base.

A new class of luminescent Cu(I) complexes with tripodal ligands – TADF emitters for the yellow to red color range.

A new class of emissive and neutral Cu(I) compounds with tripodal ligands is presented. The complexes were characterized chemically, computationally, and photophysically. Under ambient conditions, the powders of the compounds exhibit yellow to red emission with quantum yields ranging from about 5% to 35%.

The new NH-acid HN(C6F5)(C(CF3)3) and its crystalline and volatile alkaline and earth alkaline metal salts.

Herein we report on the new NH-acid N-(2,3,4,5,6-pentafluorophenyl)-N-nonafluoro-tert-butylamine, HN(C6F5)(C(CF3)3), bearing two different sterically demanding and strongly electron-withdrawing perfluorinated amine substituents. The title compound and seven of its alkaline and alkaline earth metal salts were synthesized and investigated concerning their thermal, spectroscopic, and structural properties. The Li, Na, K, Cs, and Mg salts were investigated by single-crystal XRD analysis.

Dichlorido(dimethyl sulfoxide-κS)(η-mesitylene)ruthenium(II).

The title compound, [RuCl(2)(C(9)H(12))(C(2)H(6)OS)], features a planar [maximum deviation = 0.0075 (17) Å] η(6)-bound mesitylene ligand and a dimethyl sulfoxide ligand coordinated via the S atom. The overall complex geometry about the Ru(II) atom is best described as a piano-stool configuration.