Closing the Loop in the Carbon Cycle: Enzymatic Reactions Housed in Metal-Organic Frameworks for CO Conversion to Methanol.

The preparation of value-added chemicals from carbon dioxide (CO) can act as a way of reducing the greenhouse gas from the atmosphere. Industrially significant C1 chemicals like methanol (CHOH), formic acid (HCOOH), and formaldehyde (HCHO) can be formed from CO. One sustainable way of achieving this is by connecting the reactions catalyzed by the enzymes formate dehydrogenase (FDH), formaldehyde dehydrogenase (FALDH), and alcohol dehydrogenase (ADH) into a single cascade reaction where CO is hydrogenated to CHOH.

Water sorption studies with mesoporous multivariate monoliths based on UiO-66.

Hierarchical linker thermolysis has been used to enhance the porosity of monolithic UiO-66-based metal-organic frameworks (MOFs) containing 30 wt% 2-aminoterephthalic acid (BDC-NH) linker. In this multivariate ( mixed-linker) MOF, the thermolabile BDC-NH linker decomposed at ∼350 °C, inducing mesopore formation. The nitrogen sorption of these monolithic MOFs was probed, and an increase in gas uptake of more than 200 cm g was observed after activation by heating, together with an increase in pore volume and mean pore width, indicating the creation of mesopores.

Hydrogenation of Carbon Dioxide to Formate by Noble Metal Catalysts Supported on a Chemically Stable Lanthanum Rod-Metal-Organic Framework.

The conversion of carbon dioxide to formate is of great importance for hydrogen storage as well as being a step to access an array of olefins. Herein, we have prepared a JMS-5 metal-organic framework (MOF) using a bipyridyl dicarboxylate linker, with the molecular formula [La(bpdc)(dmf)(OAc)]·dmf. The MOF was functionalized by cyclometalation using Pd(II), Pt(II), Ru(II), Rh(III), and Ir(III) complexes.

Two novel metal-organic frameworks functionalised with pentamethylcyclopentadienyl iridium(III) chloride for catalytic conversion of carbon dioxide to formate.

Hydrogenation of CO to formate is a vital reaction, because formate is an excellent hydrogen carrier, which yields blue hydrogen. Blue hydrogen is comparatively cheaper and attractive as the world envisions the hydrogen economy. In this work, two isostructural lanthanide-based MOFs (JMS-6 and JMS-7 [Ln(bpdc)(dmf)(HO)]) were prepared and used as support materials for molecular catalysts.

Selective Cu and Ni-MOFs as pre-catalysts for the hydrogenation of furfural to furfuryl alcohol.

In this work, we report the design of one-dimensional (1D) metal-organic framework containing Cu(II) and Ni(II) active sites using a ,'-bis-(4-pyridyl)isophthalamide linker to form MOF 1 [Cu(L1)(NO)·DMF] and MOF 2 [NiL1Cl]. The MOFs were evaluated as heterogeneous catalysts for the hydrogenation of furfural to furfuryl alcohol. MOF 2 catalyst showed impressive performance with conversion of FF (81%) and selectivity towards FA (100%).

The Transfer Hydrogenation of Cinnamaldehyde Using Homogeneous Cobalt(II) and Nickel(II) (E)-1-(Pyridin-2-yl)-N-(3-(triethoxysilyl)propyl)methanimine and the Complexes Anchored on FeO Support as Pre-Catalysts: An Experimental and In Silico Approach.

The imino pyridine Schiff base cobalt(II) and nickel(II) complexes ( and ) and their functionalised γ-FeO counterparts ( and ) were synthesised and characterised using IR, elemental analysis, and ESI-MS for and , and single crystal X-ray diffraction for , while the functionalised materials and were characterized using IR, XRD, SEM, TEM, EDS, ICP-OES, XPS and TGA. Complexes , and the functionalised materials and were tested as catalysts for the selective transfer hydrogenation of cinnamaldehyde and all four pre-catalysts showed excellent catalytic activity. Complexes and acted as homogeneous catalysts with high selectivity towards the formation of hydrocinnamaldehyde (88.

New Triazolyl N^N Bidentate Rh(III), Ir(III), Ru(II) and Os(II) Complexes: Synthesis and Characterization, Probing Possible Relations between Cytotoxicity with Transfer Hydrogenation Efficacy and Interaction with Model Biomolecules.

Cisplatin and other metallodrugs have realised great success in clinical chemotherapeutic applications as anticancer drugs. However, severe toxicity to healthy cells and non-selectivity to cancer cells remains a challenge, warranting the further search for alternative agents. Herein, we report the anticancer potential of a series of complexes of the general formula [MCl(p-cym)(k2-N^N-L)]+ X− and [MCl(Cp*)(k2-N^N-L)]+ X−, where M is the metal centre (Ru(II), Os(II), Rh(III) or Ir(III)), L = 1-benzyl-4-pyridinyl-1-H-1,2,3-triazole for L1 and 1-picolyl-4-pyridinyl-1-H-1,2,3-triazole for L2 and X− = Cl−, BF4−, BPh4−.

Chiral-at-Metal: Iridium(III) Tetrazole Complexes With Proton-Responsive P-OH Groups for CO Hydrogenation.

A rise in atmospheric CO levels, following years of burning fossil fuels, has brought about increase in global temperatures and climate change due to the greenhouse effect. As such, recent efforts in addressing this problem have been directed to the use of CO as a non-expensive and non-toxic single carbon, C, source for making chemical products. Herein, we report on the use of tetrazolyl complexes as catalyst precursors for hydrogenation of CO.

Synthesis and Characterization of 2D Metal-Organic Frameworks for Adsorption of Carbon Dioxide and Hydrogen.

The reaction of Cd(NO)·4HO and Zn(NO)·6HO with the bipyridyl dicarboxylate ligand Hbpydc (2,2'-bipyridine-4,4'-dicarboxylic acid) afforded two porous metal organic frameworks [Cd(bpydc)(DMF)·2DMF] (JMS-3) and [Zn(bpydc)(DMF)·DMF] (JMS-4). X-ray diffraction studies revealed that both JMS-3 and JMS-4 crystallize in the monoclinic crystal. The MOFs possess 2D interdigited networks with () topology.

Synthesis and anti-cancer activity of bis-amino-phosphine ligand and its ruthenium(II) complexes.

The development of both chemotherapeutic drug resistance as well as adverse side effects suggest that the current chemotherapeutic drugs remain ineffective in treating the various types of cancers. The development of new metallodrugs presenting anti-cancer activity is therefore needed. Ruthenium complexes have gained a great deal of interest due to their promising anti-tumour properties and reduced toxicity in vivo.

Palladium(II) Immobilized on Metal-Organic Frameworks for Catalytic Conversion of Carbon Dioxide to Formate.

In this work, we report the design of a two-dimensional (2D) isostructural metal-organic framework containing Pd(II) active sites, using a bipyridyl dicarboxylate linker (Mg(bpdc)(DMF)PdCl] (Pd@Mg:JMS-2) and [Mn(bpdc)(DMF)PdCl](Pd@Mn:JMS-2)). The activated MOFs Pd@Mg:JMS-2a and Pd@Mn:JMS-2a were evaluated as heterogeneous catalysts for the hydrogenation of carbon dioxide (CO) to formate. Under optimal conditions, the MOFs exhibited impressive catalytic activity with formate turnover numbers of 7272 and 9808 for Pd@Mg:JMS-2a and Pd@Mn:JMS-2a, respectively, after 24 h.

A Novel Series of N-aryltriazole and N-acridinyltriazole Hybrids as Potential Anticancer Agents.

Background: Triazoles are a class of aza-heterocycles with broad spectrum of biological importance. The synthetic tunability of the triazole moiety allows for the development of new pharmacophores with applications as drugs to contend with the burden of cancer.

Objective: In this study, we aimed to develop a series of N-aryltriazole and N-acridinyltriazole molecular hybrids and evaluate their potential as anticancer agents.

Cyclometalation of lanthanum(iii) based MOF for catalytic hydrogenation of carbon dioxide to formate.

The hydrogenation of carbon dioxide (CO) to formic acid is of great importance due to its useful properties in the chemical industry. In this work, we have prepared a novel metal-organic framework (MOF), JMS-1, using bipyridyl dicarboxylate linkers, with molecular formula [La(bpdc)(DMF)] . Network analysis of JMS-1 revealed a new 7-connected topology ().

Water-soluble SNS cationic palladium(II) complexes and their Suzuki-Miyaura cross-coupling reactions in aqueous medium.

Unlike their SCS analogues, SNS pincer complexes are poorly studied for their use in coupling reactions. Accordingly, a series of water soluble cationic Pd(II) SNS pincer complexes have been successfully synthesised and investigated in detail for their catalytic activity in Suzuki-Miyaura coupling reactions. By using only 0.

Synthesis, characterization and evaluation of bulky bis(pyrazolyl)palladium complexes in Suzuki-Miyaura cross-coupling reactions.

Pyrazole-containing compounds have been used in recent times as ligands to stabilize metal complexes used as pre-catalysts in cross-coupling reactions. With various substituents at various positions in the pyrazole ring, the overall electrophilic and steric properties of the metal complexes can be fine-tuned. Herein, we report the synthesis of bulky pyrazole-based ligands by condensation of methyl 4-(bromomethyl)benzoate or benzyl bromide with various substituted pyrazole compounds.

Aqueous-phase hydroformylation of 1-octene using hydrophilic sulfonate salicylaldimine dendrimers.

Water-soluble dendritic ligands based on tris-2-(5-sulfonato salicylaldimine ethyl)amine (5) and DAB-(5-sulfonato salicylaldimine) (6) (DAB = diaminobutane) were synthesized by means of Schiff base condensation and sulfonation reactions. These dendritic ligands were fully characterized by (1)H NMR, (13)C NMR and FT-IR spectroscopy, elemental analysis and mass spectrometry. Dendritic ligands (5 and 6) in combination with [RhCl(COD)](2) (COD = 1,5-cyclooctadiene) were evaluated in aqueous biphasic hydroformylation of 1-octene.

Hydroformylation of 1-octene using low-generation Rh(I) metallodendritic catalysts based on a tris-2-(2-pyridyliminoethyl)amine scaffold.

The synthesis and characterization of low-generation pyridylimine Rh(I) metallodendrimers is described. These metallodendrimers were obtained via a Schiff base condensation of tris-2-(aminoethyl)amine with 2-pyridinecarboxaldehyde to afford the tris-2-(2-pyridylimine ethyl) amine ligand (1). Subsequent complexation reactions with [RhCl(CO)(2)](2) and [RhCl(COD)](2) yielded the corresponding metal-containing dendrimers containing -RhCl(CO) and -Rh(COD) moieties on the periphery.