Assignment of individual structures from intermetalloid nickel gallium cluster ensembles.

Poorly selective mixed-metal cluster synthesis and separation yield reaction solutions of inseparable intermetalloid cluster mixtures, which are often discarded. High-resolution mass spectrometry, however, can provide precise compositional data of such product mixtures. Structure assignments can be achieved by advanced computational screening and consideration of the complete structural space. Here, we experimentally verify structure and composition of a whole cluster ensemble by combining a set of spectroscopic techniques. Our study case are the very similar nickel/gallium clusters of M12, M13 and M14 core composition Ni6+xGa6+y (x + y ≤ 2). The rationalization of structure, bonding and reactivity is built upon the organometallic superatom cluster [Ni6Ga6](Cp*)6 = [Ga6](NiCp*)6 (1; Cp* = C5Me5). The structural conclusions are validated by reactivity tests using carbon monoxide, which selectively binds to Ni sites, whereas (triisopropylsilyl)acetylene selectively binds to Ga sites.

Understanding and Controlling Molecular Compositions and Properties in Mixed-Linker Porphyrin Metal-Organic Frameworks.

Porphyrin-based metal-organic frameworks (MOFs) are attractive materials for photo- and thermally activated catalysis due to their unique structural features related to the porphyrin moiety, guest-accessible porosity, and high chemical tunability. In this study, we report the synthetic incorporation of nonplanar ß-ethyl-functionalized porphyrin linkers into the framework structure of PCN-222, obtaining a solid-solution series of materials with different modified linker contents. Comprehensive analysis by a combination of characterization techniques, such as NMR, UV-vis and IR spectroscopy, powder X-ray diffraction, and N2 sorption analysis, allows for the confirmation of linker incorporation. A detailed structural analysis of intrinsic material properties, such as the thermal response of the different materials, underlines the complexity of synthesizing and understanding such materials. This study presents a blueprint for synthesizing and analyzing porphyrin-based mixed-linker MOF systems and highlights the hurdles of characterizing such materials.

Catalytic Alkyne Semihydrogenation with Polyhydride Ni/Ga Clusters.

The bimetallic, decanuclear Ni3 Ga7 -cluster of the formula [Ni3 (GaTMP)3 (µ2 -GaTMP)3 (µ3 -GaTMP)] (1, TMP=2,2,6,6-tetramethylpiperidinyl) reacts reversibly with dihydrogen under the formation of a series of (poly-)hydride clusters 2. Low-temperature 2D NMR experiments at -80 °C show that 2 consist of a mixture of a di- (2Di ), tetra- (2Tetra ) and hexahydride species (2Hexa ). The structures of 2Di and 2Tetra are assessed by a combination of 2D NMR spectroscopy and DFT calculations. The cooperation of both metals is essential for the high hydrogen uptake of the cluster. Polyhydrides 2 are catalytically active in the semihydrogenation of 4-octyne to 4-octene with good selectivity. The example is the first of its kind and conceptually relates properties of molecular, atom-precise transition metal/main group metal clusters to the respective solid-state phase in catalysis.

Topology- and wavelength-governed CO2 reduction photocatalysis in molecular catalyst-metal-organic framework assemblies.

Optimising catalyst materials for visible light-driven fuel production requires understanding complex and intertwined processes including light absorption and catalyst stability, as well as mass, charge, and energy transport. These phenomena can be uniquely combined (and ideally controlled) in porous host-guest systems. Towards this goal we designed model systems consisting of molecular complexes as catalysts and porphyrin metal-organic frameworks (MOFs) as light-harvesting and hosting porous matrices. Two MOF-rhenium molecule hybrids with identical building units but differing topologies (PCN-222 and PCN-224) were prepared including photosensitiser-catalyst dyad-like systems integrated via self-assembled molecular recognition. This allowed us to investigate the impact of MOF topology on solar fuel production, with PCN-222 assemblies yielding a 9-fold turnover number enhancement for solar CO2-to-CO reduction over PCN-224 hybrids as well as a 10-fold increase compared to the homogeneous catalyst-porphyrin dyad. Catalytic, spectroscopic and computational investigations identified larger pores and efficient exciton hopping as performance boosters, and further unveiled a MOF-specific, wavelength-dependent catalytic behaviour. Accordingly, CO2 reduction product selectivity is governed by selective activation of two independent, circumscribed or delocalised, energy/electron transfer channels from the porphyrin excited state to either formate-producing MOF nodes or the CO-producing molecular catalysts.

Vectorial Catalysis in Surface-Anchored Nanometer-Sized Metal-Organic Frameworks-Based Microfluidic Devices.

Vectorial catalysis-controlling multi-step reactions in a programmed sequence and by defined spatial localization in a microscale device-is an enticing goal in bio-inspired catalysis research. However, translating concepts from natural cascade biocatalysis into artificial hierarchical chemical systems remains a challenge. Herein, we demonstrate integration of two different surface-anchored nanometer-sized metal-organic frameworks (MOFs) in a microfluidic device for modelling vectorial catalysis. Catalyst immobilization at defined sections along the microchannel and a two-step cascade reaction was conducted with full conversion after 30 seconds and high turnover frequencies (TOF≈105  h-1 ).

Nanometallurgy in solution: organometallic synthesis of intermetallic Pd-Ga colloids and their activity in semi-hydrogenation catalysis.

Nanoparticles (NPs) of Pd1--xGax (x = 0.67, 0.5, 0.33), stabilized in non-aqueous colloidal solution, were obtained via an organometallic approach under mild conditions using [Pd2(dvds)3] and GaCp* as all-hydrocarbon ligated metal-precursor compounds (dvds = 1,1,3,3-tetramethyl-1,3-divinyl-disiloxane; Cp* = η5-C5Me5; Me = CH3). The reaction of the two precursors involves the formation of a library of molecular clusters [PdnGamCp*y(dvds)z], as shown by liquid injection field desorption ionization mass spectrometry (LIFDI-MS). Full characterization of the catalytic system (HR-TEM, EDX, DLS, PXRD, XPS, NMR, IR, Raman) confirmed the formation of ultra-small, spherical NPs with narrow size distributions ranging from 1.2 ± 0.2 nm to 2.1 ± 0.4 nm (depending on the Pd : Ga ratio). The catalytic performance of the Pd1--xGax NPs in the semi-hydrogenation of terminal and internal alkynes and the influence of the gallium content on product selectivity were investigated. The highest activities (65%) and selectivities (81%) are achieved using colloids with a "stoichiometric" Pd/Ga ratio of 1 : 1 at 0 °C and 2.0 bar H2 pressure. While lower Ga ratios lead to an increase in activity, higher Ga contents increase the olefin selectivity but are detrimental to the activity.

Defect Engineering of Copper Paddlewheel-Based Metal-Organic Frameworks of Type NOTT-100: Implementing Truncated Linkers and Its Effect on Catalytic Properties.

A series of new defect-engineered metal-organic frameworks (DEMOFs) were synthesized by framework doping with truncated linkers employing the mixed-linker approach. Two tritopic defective (truncated) linkers, biphenyl-3,3',5-tricarboxylates (LH) lacking a ligating group and 5-(5-carboxypyridin-3-yl)isophthalates (LPy) bearing a weaker interacting ligator site, were integrated into the framework of Cu2(BPTC) (NOTT-100, BPTC = biphenyl-3,3',5,5'-tetracarboxylates). Incorporating LH into the framework mainly generates missing metal node defects, thereby obtaining dangling COOH groups in the framework. However, introducing LPy forms more modified metal nodes featuring reduced and more accessible Cu sites. In comparison with the pristine NOTT-100, the defect-engineered NOTT-100 (DE-NOTT-100) samples show two unique features: (i) functional groups (the protonated carboxylate groups as the Brønsted acid sites or the pyridyl N atoms as the Lewis basic sites), which can act as second active sites, are incorporated into the MOF frameworks, and (ii) more modified paddlewheels, which provided extra coordinatively unsaturated sites, are generated. The cooperative functioning of the above characteristics enhances the catalytic performance of certain types of reactions. For a proof of concept, two exemplary reactions, namely, the cycloaddition of CO2 with propylene oxide to propylene carbonate and the cyclopropanation of styrene, were carried out to evaluate the catalytic activities of those DE-NOTT-100 materials depending on the defect structure.

Determination of the Critical Micelle Concentration of Imidazolium Ionic Liquids in Aqueous Hydrogen Peroxide.

The critical micelle concentrations (CMCs) of several imidazolium-based ionic liquids (ILs) in aqueous H2O2 (50 wt % in H2O) were determined by tensiometry, conductometry, and the rate of catalytic epoxidation of cis-cyclooctene. CMC values in aqueous H2O2 were significantly lower compared to values in pure water. In both H2O2 solution and water, the CMC of all ILs decreases with an increasing alkyl chain length and increases with a rising temperature. The degree of micelle ionization of 1-methyl-3-octylimidazolium tetrafluoroborate ([OMIM][BF4]) was calculated by conductometry in a temperature range of 22-70 °C.

Generation and Stabilization of Small Platinum Clusters Pt12±x Inside a Metal-Organic Framework.

The generation and matrix stabilization of ligand-free, small platinum nanoclusters (NCs) Pt12±x is presented. The metal-organic framework-template approach is based on encapsulating CO-ligated, atom-precise Pt9 Chini clusters [{Pt3(CO)6}3]2- into the zeolitic imidazolate framework ZIF-8. The selective formation of the air-stable inclusion compound [NBu4]2[{Pt3(CO)6}4]@ZIF-8 of defined atomicity Pt12 and with Pt loadings of 1-20 wt % was monitored by UV/vis and IR spectroscopy and was confirmed by high-resolution transmission electron microscopy (HR-TEM), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), X-ray photoelectron spectroscopy (XPS), and powder X-ray diffraction (PXRD). Thermally induced decarbonylation at 200 °C yields the composite material Ptn@ZIF-8 with a cluster atomicity n close to 12, irrespective of the Pt loading. The PtNCs retain their size even during annealing at 300 °C for 24 h and during catalytic hydrogenation of 1-hexene at 25 °C in the liquid phase. The Ptn@ZIF-8 material can conveniently be used for storing small PtNCs and their further processing. Removal of the protective ZIF-8 matrix under acidic conditions and transfer of the PtNCs to carbon substrates yields defined aggregation to small Pt nanoparticles (1.14 ± 0.35 nm, HR-TEM), which have previously shown exceptional performance in the electrocatalytic oxygen reduction reaction (ORR).

Optimizing the Size of Platinum Nanoparticles for Enhanced Mass Activity in the Electrochemical Oxygen Reduction Reaction.

High oxygen reduction (ORR) activity has been for many years considered as the key to many energy applications. Herein, by combining theory and experiment we prepare Pt nanoparticles with optimal size for the efficient ORR in proton-exchange-membrane fuel cells. Optimal nanoparticle sizes are predicted near 1, 2, and 3 nm by computational screening. To corroborate our computational results, we have addressed the challenge of approximately 1 nm sized Pt nanoparticle synthesis with a metal-organic framework (MOF) template approach. The electrocatalyst was characterized by HR-TEM, XPS, and its ORR activity was measured using a rotating disk electrode setup. The observed mass activities (0.87±0.14 A mgPt -1 ) are close to the computational prediction (0.99 A mgPt -1 ). We report the highest to date mass activity among pure Pt catalysts for the ORR within similar size range. The specific and mass activities are twice as high as the Tanaka commercial Pt/C catalysis.

Hydrogen Production and Storage on a Formic Acid/Bicarbonate Platform using Water-Soluble N-Heterocyclic Carbene Complexes of Late Transition Metals.

The synthesis and characterization of two water-soluble bis-N-heterocyclic carbene (NHC) complexes of rhodium and iridium is presented. Both compounds are active in H2 generation from formic acid and in hydrogenation of bicarbonate to formate. The rhodium derivative is most active in both reactions, reaching a TOF of 39 000 h-1 and a TON of 449 000 for H2 production. The catalytic hydrogenation reactions were carried out in an autoclave system and analyzed using the integrated peak areas in the 1 H NMR spectra. Decomposition of formic acid was investigated using a Fisher-Porter bottle equipped with a pressure transducer. Long-term stability for hydrogen evolution was tested by surveillance of the gas flow rate. The procedure does not require any additives like amines or inert gas conditions. Density functional theory calculations in agreement with experimental results suggest a bicarbonate reduction mechanism involving a second catalyst molecule, which provides an external hydride acting as reducing agent.

Functionalization of small platinum nanoparticles with amines and phosphines: Ligand binding modes and particle stability.

We report the binding mode of amines and phosphines on platinum nanoparticles. Protective ligands comprising different functional groups are systematically studied for the elucidation of ligand binding at different functionalization conditions. From the functionalization conditions it is concluded that the binding of amines to the nanoparticles occurs via the formation of a PtHN moiety or electrostatic interaction, which is supported by spectroscopic evidences. In particular from complex chemistry such a binding mode is surprising, as amines are expected to bind via their electron pair to the metal. Similar results from functionalization are observed for phosphine-protected nanoparticles, which suggest similar binding modes in these systems. In contrast to the strong covalent bond of the protection with thiols, considerable weakly binding systems result. The characteristics of the binding mode are reflected by the stability of the colloids and their catalytic properties. In the selective hydrogenation of 3-hexyne to 3-hexene thiolate-stabilized Pt particles are highly stable, but exhibit the lowest activity. On the other hand, amine- and phosphine-capped platinum nanoparticles show a significantly higher activity, but rapidly agglomerate.

Olefin Epoxidation in Aqueous Phase Using Ionic-Liquid Catalysts.

Hydrophobic imidazolium-based ionic liquids (IL) act as catalysts for the epoxidation of unfunctionalized olefins in water using hydrogen peroxide as oxidant. Although the catalysts are insoluble in both the substrate and in water, surprisingly, they are very well soluble in aqueous H2 O2 solution, owing to perrhenate-H2 O2 interactions. Even more remarkably, the presence of the catalyst also boosts the solubility of substrate in water. This effect is crucially dependent on the cation design. Hence, the imidazolium perrhenates enable both the transfer of hydrophobic substrate into the aqueous phase, and serve as actual catalysts, which is unprecedented. At the end of the reaction and in absence of H2 O2 the IL catalyst forms a third phase next to the lipophilic product and water and can easily be recycled.

Binding of molecular oxygen by an artificial heme analogue: investigation on the formation of an Fe-tetracarbene superoxo complex.

The dioxygen reactivity of a cyclic iron(ii) tetra-NHC-complex (NHC: N-heterocyclic carbene) is investigated. Divergent oxidation behavior is observed depending on the choice of the solvent (acetonitrile or acetone). In the first case, exposure to molecular oxygen leads to an oxygen free Fe(iii) whereas in the latter case an oxide bridged Fe(iii) dimer is formed. In acetone, an Fe(iii)-superoxide can be trapped, isolated and characterized as intermediate at low temperatures. An Fe(iii)-O-Fe(iii) dimer is formed from the Fe(iii) superoxide in acetone upon warming and the molecular structure has been revealed by single crystal X-ray diffraction. It is shown that the oxidation of the Fe(ii) complex in both solvents is a reversible process. For the regeneration of the initial Fe(ii) complex both organic and inorganic reducing agents can be used.

Oxidative degradation of the organometallic iron(II) complex [Fe{bis[3-(pyridin-2-yl)-1H-imidazol-1-yl]methane}(MeCN)(PMe3)](PF6)2: structure of the ligand decomposition product trapped via coordination to iron(II).

Iron is of interest as a catalyst because of its established use in the Haber-Bosch process and because of its high abundance and low toxicity. Nitrogen-heterocyclic carbenes (NHC) are important ligands in homogeneous catalysis and iron-NHC complexes have attracted increasing attention in recent years but still face problems in terms of stability under oxidative conditions. The structure of the iron(II) complex [1,1'-bis(pyridin-2-yl)-2,2-bi(1H-imidazole)-κN(3)][3,3'-bis(pyridin-2-yl-κN)-1,1'-methanediylbi(1H-imidazol-2-yl-κC(2))](trimethylphosphane-κP)iron(II) bis(hexafluoridophosphate), [Fe(C17H14N6)(C16H12N6)(C3H9P)](PF6)2, features coordination by an organic decomposition product of a tetradentate NHC ligand in an axial position. The decomposition product, a C-C-coupled biimidazole, is trapped by coordination to still-intact iron(II) complexes. Insights into the structural features of the organic decomposition products might help to improve the stability of oxidation catalysts under harsh conditions.

Fighting Fenton Chemistry: A Highly Active Iron(III) Tetracarbene Complex in Epoxidation Catalysis.

Organometallic Fe complexes with exceptionally high activities in homogeneous epoxidation catalysis are reported. The compounds display Fe(II) and Fe(III) oxidation states and bear a tetracarbene ligand. The more active catalyst exhibits activities up to 183 000 turnovers per hour at room temperature and turnover numbers of up to 4300 at -30 °C. For the Fe(III) complex, a decreased Fenton-type reactivity is observed compared with Fe(II) catalysts reported previously as indicated by a substantially lower H2 O2 decomposition and higher (initial) turnover frequencies. The dependence of the catalyst performance on the catalyst loading, substrate, water addition, and the oxidant is investigated. Under all applied conditions, the advantageous nature of the use of the Fe(III) complex is evident.

Formation of Highly Strained N-Heterocycles via Decomposition of Iron N-Heterocyclic Carbene Complexes: The Value of Labile Fe-C Bonds.

An unusual, highly-strained annulated 2,2'-biimdazole was isolated as decomposition product of the outer-sphere one-electron oxidation of an iron(II) N-heterocyclic carbene (NHC) complex bearing a tetradentate bis(NHC)-bis- (pyridine) ligand (NCCN). Reductive elimination leading to the 2,2'-biimdazole is a consequence of the lability of the FeC bonds in the transient species and also extends to complexes with modified ligands but the same coordination geometry. Closely related by a two-electron redox step to a family of less-strained tetraazafulvalenes, the obtained 2,2'-biimidazolium salts were studied electrochemically. Introduction of methyl substituents at the methylene tether significantly increased the reversibility of the electrochemical reduction. Furthermore, the reactivity of the 2,2'-biimidazolium salt was examined by oxidative addition of [Ni(cod)2 ] to the central CC bond, providing a previously unknown way for the formation of NHC transition metal complexes.

Immobilisation of a molecular epoxidation catalyst on UiO-66 and -67: the effect of pore size on catalyst activity and recycling.

Amino-functionalised metal-organic frameworks UiO-66 and -67 were post-synthetically modified with salicylaldehyde. A molybdenum complex was immobilised on the resulting materials. They were characterised by (13)C-MAS-NMR, XPS and PXRD to confirm immobilisation and stability. The immobilised complex is an active and reusable catalyst for olefin epoxidation with tert-butyl hydroperoxide (TBHP) as an oxidant. It is shown that the effective pore size, probed with Brunauer-Emmett-Teller (BET) surface area analysis and the number of amino groups affect the diffusion of reactants and products, as well as catalyst recycling.

Structure and spectroscopic properties of the dimeric copper(I) N-heterocyclic carbene complex [Cu2(CNC(t-Bu))2](PF6)2.

In recent years, the use of copper N-heterocyclic carbene (NHC) complexes has expanded to fields besides catalysis, namely medicinal chemistry and luminescence applications. In the latter case, multinuclear copper NHC compounds have attracted interest, however, the number of these complexes in the literature is still quite limited. Bis[µ-1,3-bis(3-tert-butylimidazolin-2-yliden-1-yl)pyridine]-1κ(4)C(2),N:N,C(2');2κ(4)C(2),N:N,C(2')-dicopper(I) bis(hexafluoridophosphate), [Cu2(C19H25N5)2](PF6)2, is a dimeric copper(I) complex bridged by two CNC, i.e. bis(N-heterocyclic carbene)pyridine, ligands. Each Cu(I) atom is almost linearly coordinated by two NHC ligands and interactions are observed between the pyridine N atoms and the metal centres, while no cuprophilic interactions were observed. Very strong absorption bands are evident in the UV-Vis spectrum at 236 and 274 nm, and an emission band is observed at 450 nm. The reported complex is a new example of a multinuclear copper NHC complex and a member of a compound class which has only rarely been reported.

Structural diversity of late transition metal complexes with flexible tetra-NHC ligands.

The synthesis of copper, gold, nickel, palladium, platinum, and iron complexes with open chain tetra-N-heterocyclic carbene (NHC) ligands via transmetalation using silver NHC complexes is presented. The obtained complexes show differing coordination geometries depending on both ligand structure and metal. While the complexes of the coinage metals form di- or tetranuclear structures, the group 10 metal complexes exhibit a distorted square planar coordination geometry at the metal centers. In the case of iron an enhanced flexibility of the ligand - caused by a longer alkyl bridge - leads to octahedral complexes with a sawhorse-type coordination by the tetracarbene ligand and two cis acetonitrile ligands. To the best of our knowledge, this is the first known example of a tetracarbene ligand in sawhorse-type coordination within an octahedral coordination sphere. The remaining cis-labile sites are prone to exchange reactions as shown by addition of trimethylphosphine.