A plethora of methods have been developed over the years so that carbon dioxide can be used as a reactant in organic synthesis. Given the abundance of this compound, its utilization in synthetic chemistry, particularly on an industrial scale, is still at a rather low level. In the last 35 years, considerable research has been performed to find catalytic routes to transform CO(2) into carboxylic acids, esters, lactones, and polymers in an economic way. This Review presents an overview of the available homogeneous catalytic routes that use carbon dioxide as a C(1) carbon source for the synthesis of industrial products as well as fine chemicals.

The gas-phase loading of [Zn4O(bdc)3] (MOF-5; bdc = 1,4-benzenedicarboxylate) with the volatile compound [Ru(cod)(cot)] (cod = 1,5-cyclooctadiene, cot = 1,3,5-cyclooctatriene) was followed by solid-state (13)C magic angle spinning (MAS) NMR spectroscopy. Subsequent hydrogenolysis of the adsorbed complex inside the porous structure of MOF-5 at 3 bar and 150 degrees C was performed, yielding ruthenium nanoparticles in a typical size range of 1.5-1.7 nm, embedded in the intact MOF-5 matrix, as confirmed by transmission electron microscopy (TEM), selected area electron diffraction (SAED), powder X-ray diffraction (PXRD), and X-ray absorption spectroscopy (XAS). The adsorption of CO molecules on the obtained Ru@MOF-5 nanocomposite was followed by IR spectroscopy. Solid-state (2)H NMR measurements indicated that MOF-5 was a stabilizing support with only weak interactions with the embedded particles, as deduced from the surprisingly high mobility of the surface Ru-D species in comparison to surfactant-stabilized colloidal Ru nanoparticles of similar sizes. Surprisingly, hydrogenolysis of the [Ru(cod)(cot)]3.5@MOF-5 inclusion compound at the milder condition of 25 degrees C does not lead to the quantitative formation of Ru nanoparticles. Instead, formation of a ruthenium-cyclooctadiene complex with the arene moiety of the bdc linkers of the framework takes place, as revealed by (13)C MAS NMR, PXRD, and TEM.

The synthesis of cyclic carbonates through coupling of carbon dioxide with epoxides is 100 % atom economical and is already performed on an industrial scale. Its impact regarding the use of carbon dioxide as a renewable carbon source is expected to grow significantly in the near future, so that the development of efficient catalysts is of high interest in academia and industry. To improve the carbon footprint and sustainability of the cycloaddition reaction, the use of organocatalytic methods is a promising approach. Herein, available metal-free catalysts for the preparation of cyclic carbonates are described and elaborated concerning the overall sustainability of the process. Therefore, the required reaction conditions, as well as the activity of the catalysts and their reusability, are compared and evaluated. In addition to ammonium-, phosphonium-, or imidazolium-based single-component catalysts and their supported analogues, the growing field of research concerning dual catalysts are also discussed in detail.

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Metal-organic frameworks (MOF) are becoming a more and more important class of functional materials. Yet, very often, the synthesis of MOFs is not easy to control and requires a profound knowledge and experience in solid state chemistry. One of the most frequently used metal connectors is the so-called 'paddle-wheel' (PW) unit, which is a well-known molecular compound type in inorganic coordination chemistry. Depending on the ligands, the geometry of PWs strictly directs the assembly of ordered networks. This review focuses on the question, to what extent ordered network structures can be accessed by typical molecular syntheses in solution, starting from molecular PW complexes to ordered macromolecules, finite cage compounds and finally, three-dimensional superstructures.

The coordination of low-valent group 13 organyls E I R [E = Al, Ga, In; R = Cp*, C(SiMe 3 ) 3 ] to transition metals has attracted increasing interest over the past decade. Complexes and cluster compounds of these new ligands with a number of transition metals have been isolated and characterised. The E I R moiety is formally isolobal with CO and PR 3 (R = alkyl, Cp*) or carbenes (R = chelating group) with varying σ-donor and π-acceptor properties depending on the organic group R

An iron(II) complex with a cyclic tetradentate ligand containing four N-heterocyclic carbenes was synthesized and characterized by means of NMR and IR spectroscopies, as well as by single-crystal X-ray structure analysis. The iron center exhibits an octahedral coordination geometry with two acetonitrile ligands in axial positions, showing structural analogies with porphyrine-ligated iron complexes. The acetonitrile ligands can readily be substituted by other ligands, for instance, dimethyl sulfoxide, carbon monoxide, and nitric oxide. Cyclic voltammetry was used to examine the electronic properties of the synthesized compounds.

This work reports on iron-catalysed hydroxylation of benzene and toluene using aqueous H2O2. While benzene is hydroxylated with a high selectivity to phenol, toluene is hydroxylated to cresols with a high selectivity for the ortho and para-position. An inverse KIE indicates the presence of a high valent Fe=O species during catalysis.