Solubilizing Metal-Organic Frameworks for an In Situ IR-SEC Study of a CO2 Reduction Catalyst.

Metal-organic frameworks (MOFs) are typically assembled by bridging metal centers with organic linkers for various applications, including providing robust support for heterogeneous catalysts for CO2 reduction. In this study, we have demonstrated the solubilization of a MOF tethered to a CO2-reducing electrocatalyst and studied its fundamental electrochemistry in THF solvent using infrared spectroelectrochemistry (IR-SEC). The fundamental electrochemical properties of this immobilized catalyst were compared to that of its homogeneous counterpart. This approach provides a foundation for future experimental studies to bridge the gap between homogeneous and heterogeneous electrocatalysis.

Transition Metal Pyrithione Complexes (Ni, Mn, Fe, and Co) as Electrocatalysts for Proton Reduction of Acetic Acid.

A series of mononuclear first-row transition metal pyrithione M(pyr) n complexes (M = Ni(II), Mn(II), n = 2; M = Co(III), Fe(III), n = 3) have been prepared from the reaction of the corresponding metal salt with the sodium salt of pyrithione. Using cyclic voltammetry, the complexes have been shown to behave as proton reduction electrocatalysts albeit with varying efficiencies in the presence of acetic acid as the proton source in acetonitrile. The nickel complex displays the optimal overall catalytic performance with an overpotential of 0.44 V. An ECEC mechanism is suggested for the nickel-catalyzed system based on the experimental data and supported by density functional theory calculations.

Manganese Tricarbonyl Diimine Bromide Complexes as Electrocatalysts for Proton Reduction.

Manganese tricarbonyl diimine complexes bearing pyridine and imidazole ligands have been prepared as electrocatalysts for proton reduction using acetic acid as the proton source. The electron-donor ability of the diimine ligand is found to play an important role in determining the efficiency of the electrocatalysts with [MnBr(pybz)(CO)3] (pybz = 2-(2-pyridyl)benzimidazole) exhibiting the lowest overpotential (0.28 V) toward proton reduction. The [Mn(pybz)(CO)3(MeCN)]+ cationic complex prepared via debromination of [MnBr(pybz)(CO)3] by a silver salt has also been shown to catalyze proton reduction upon its electrochemical reduction. A neutral complex [Mn(pyridine-benzimidazolate)(CO)3(MeCN)], which can be synthesized by reacting [MnBr(pybz)(CO)3] with a strong base, has been detected using IR-SEC (infrared spectroelectrochemistry) as an intermediate species in the catalytic process. Using [MnBr(pybz)(CO)3] as the model electrocatalyst, we have carried out density functional calculations to propose a proton reduction mechanism consistent with our experimental observations.

Dithiolato-Bridged Nickel(II) Salicylcysteamine Complexes as Robust Proton Reduction Electrocatalysts: Cyclic Voltammetry and Computational Studies.

A series of Schiff-base nickel(II) complexes were prepared from the reaction of nickel(II) acetate with N-salicylcysteamine [HO-C6H4-CH═N(CH2)2SH] ligands. These complexes were analyzed to be dimeric nickel complexes containing two bridging thiolato ligands. Using cyclic voltammetry, they were found to be efficient homogeneous proton reduction electrocatalysts when acetic acid was used as the proton source in acetonitrile. Catalysis was triggered upon electrochemical reduction of the nickel complex. In particular, rate constants (kobs) in the range of 104 s-1 at moderate overpotentials of 0.5-0.6 V were achieved when chloro- or bromo-containing nickel complexes were used. Combined with the experimental data, density functional theory calculations lent support to an ECEC mechanism, with the first electrochemical reduction step contributing significantly to the rate-determining step.

Bis(cyclopentadienyl)nickel(II) µ-Thiolato Complexes as Proton Reduction Electrocatalysts.

Thiolato-bridged cyclopentadienylnickel dimeric complexes have been prepared and found to be efficient and robust proton reduction electrocatalysts using acetic acid as the proton source. From cyclic voltammetry studies, moderate overpotentials of around 0.6 V and ic/ip values from 7.8 to 12.2 have been determined for 20 equiv of acetic acid at a scan rate of 100 mV/s. A turnover number of around 7 has been determined for each of the nickel complexes. The thiolato substituent of the complex does not appear to influence the catalysis significantly. Each of the nickel complexes acts as a robust homogeneous catalyst that could sustain continuous proton reduction for hours. On the basis of the experimental data, an electrochemical-chemical-electrochemical-chemical mechanism describing the catalytic process has been proposed as well.

Electrocatalytic proton reduction by an air-stable nickel(ii)-thiolato PNN pincer complex.

We report an air-stable nickel(ii)-thiolato PNN pincer complex [(PNN)NiII(SC6H4Me)]+[MeC6H4SO3]- (PNN = 2-((di-tert-butylphosphinomethyl-6-diethylaminomethyl)pyridine)) which is capable of reducing protons at an overpotential of 0.54 V at low acid concentrations. The proton reduction can be catalysed using weak or strong acids such as acetic acid and trifluoroacetic acid respectively. In contrast, the chloro and nitrate derivatives of the nickel pincer complex behave as poorer catalysts. A mechanism accounting for the role of the ligand in proton reduction is also briefly outlined.

Ancillary Ligand Effects upon the Photochemistry of Mn(bpy)(CO)3X Complexes (X = Br-, PhCC-).

The photochemistry of two Mn(bpy)(CO)3X complexes (X = PhCC-, Br-) has been studied in the coordinating solvents THF (terahydrofuran) and MeCN (acetonitrile) employing time-resolved infrared spectroscopy. The two complexes are found to exhibit strikingly different photoreactivities and solvent dependencies. In MeCN, photolysis of 1-(CO)(Br) [1 = Mn(bpy)(CO)2] affords the ionic complex [1-(MeCN)2]Br as a final product. In contrast, photolysis of 1-(CO)(CCPh) in MeCN results in facial to meridional isomerization of the parent complex. When THF is used as solvent, photolysis results in facial to meridional isomerization in both complexes, though the isomerization rate is larger for X = Br-. Pronounced differences are also observed in the photosubstitution chemistry of the two complexes where both the rate of MeCN exchange from 1-(MeCN)(X) by THFA (tetrahydrofurfurylamine) and the nature of the intermediates generated in the reaction are dependent upon X. DFT calculations are used to support analysis of some of the experiments.

Highly-phosphorescent tungsten(0) carbonyl pyridyl-imidazole complexes as photosensitisers.

Photoluminescence data are reported for two W(CO)4L complexes (L = 2-(1H-imidazol-2-yl)pyridine and 2-(2'-pyridyl)benzimidazole) in room-temperature solutions. The bidentate ligands consist of a pyridine and an imidazole moiety connected by a C-C bond. The complexes have been found to exhibit enhanced phosphorescence from the metal-to-ligand charge transfer (MLCT) excited state with quantum yields in the order of 10-3, almost two orders of magnitude higher than those reported for W(CO)4(diimine) complexes. One of the complexes W(CO)4(2-(2'-pyridyl)benzimidazole) can serve as an efficient visible-light photosensitiser for the isomerisation of aromatic alkenes with efficiency comparable to and even exceeding that of the well-studied ruthenium tris-bipyridine complex, Ru(bpy)Cl2.

A Robust Pentacoordinated Iron(II) Proton Reduction Catalyst Stabilized by a Tripodal Phosphine.

A pentacoordinated triphosphine benzenedithiolatoiron(II) complex containing a vacant site for binding has been prepared and characterized. The complex is found to be a robust proton reduction catalyst with an overpotential of 0.56 V and a turnover frequency of 2900 s-1 with respect to 0.28 M acetic acid as the proton source. A mechanism describing the electroproton reduction process has been proposed.

Intramolecular C-C Bond Coupling of Nitriles to a Diimine Ligand in Group 7 Metal Tricarbonyl Complexes.

Dissolution of M(CO)3(Br)(L(Ar)) [L(Ar) = (2,6-Cl2-C6H3-NCMe)2CH2] in either acetonitrile [M = Mn, Re] or benzonitrile (M = Re) results in C-C coupling of the nitrile to the diimine ligand. When reacted with acetonitrile, the intermediate adduct [M(CO)3(NCCH3)(L(Ar))]Br forms and undergoes an intramolecular C-C coupling reaction between the nitrile carbon and the methylene carbon of the ß-diimine ligand.

Electrocatalytic proton reduction catalyzed by a dimanganese disulfide carbonyl complex containing a redox-active internal disulfide bond.

A dimanganese hexacarbonyl complex [(Mn(CO)3)2(µ-SC6H4-o-S-S-C6H4-o-µ-S-)] containing an elongated disulfide bond electrocatalyses proton reduction at moderate overpotentials of 0.55 to 0.65 V. Cyclic voltammetric, infrared spectroscopy and computational studies suggest that the redox-active sulfur atoms of the disulfide bond serve as the initial reduction site.

Reuleaux triangle disks: new shape on the block.

We report here the unprecedented preparation of Reuleaux triangle disks. The hydrolysis and precipitation of bismuth nitrate in an ethanol-water system with 2,3-bis(2-pyridyl)pyrazine yielded basic bismuth nitrate Reuleaux triangle disks. Analysis of the intermediates provided insights into the mystery behind the formation of the Reuleaux triangle disk, revealing a unique growth process. The report of a facile method to prepare crystals of a novel shape in high yield, with good homogeneity, and with excellent reproducibility is expected to unlock new research directions in multiple disciplines.

Colloidal beading: sonication-induced stringing of selenium particles.

We report the preparation of monodispersed Se colloidal aggregates (dimers and trimers) via sonication-induced aggregation of spherical monomers. Control over the size and morphology of the products was achieved by changing the aging and sonication times, respectively. The possible mechanisms for the formation of colloidal aggregates were discussed. This method can provide a simple and versatile approach to the production of colloidal molecules of particles composed of different materials, which will be useful for fundamental studies related to colloidal systems.

A novel iron complex for highly efficient catalytic hydrogen generation from the hydrolysis of organosilanes.

Hydrolytic oxidation of organosilanes based on an iron catalyst is described for the first time. The novel iron complex, [Fe(C6H5N2O)(CO)(MeCN)3][PF6], exhibits excellent mediating power in the catalytic hydrolysis of organosilanes to produce dihydrogen and organosilanols with turnover numbers approaching 10(4) and turnover frequencies in excess of 10(2) min(-1) under ambient conditions.

Electrocatalytic hydrogen generation by a trithiolato-bridged dimanganese hexacarbonyl anion with a turnover frequency exceeding 40,000 s(-1).

An unusual ionic manganese model complex [Mn(bpy)3](+)[(CO)3Mn(µ-SPh)3Mn(CO)3](-)(bpy: 2,2'-bipyridine) has been synthesized, which bears some structural resemblance to the active site of [FeFe] hydrogenase. An overpotential of 0.61 V has been determined for the electrocatalytic proton reduction using this complex in CH3CN with CF3COOH as the proton source. A turnover frequency of 44,600 s(-1) is achieved at high scan rates and in the presence of a large amount of acid.

Thermal and photochemical reactivity of manganese tricarbonyl and tetracarbonyl complexes with a bulky diazabutadiene ligand.

The manganese tricarbonyl complex fac-Mn(Br)(CO)3((i)Pr2Ph-DAB) (1) [(i)Pr2Ph-DAB = (N,N'-bis(2,6-di-isopropylphenyl)-1,4-diaza-1,3-butadiene)] was synthesized from the reaction of Mn(CO)5Br with the sterically encumbered DAB ligand. Compound 1 exhibits rapid CO release under low power visible light irradiation (560 nm) suggesting its possible use as a photoCORM. The reaction of compound 1 with TlPF6 in the dark afforded the manganese(I) tetracarbonyl complex, [Mn(CO)4((i)Pr2Ph-DAB)][PF6] (2). While 2 is comparatively more stable than 1 in light, it demonstrates high thermal reactivity such that dissolution in CH3CN or THF at room temperature results in rapid CO loss and formation of the respective solvate complexes. This unusual reactivity is due to the large steric profile of the DAB ligand which results in a weak Mn-CO binding interaction.

[Cp*IrCl2]2 catalyzed formation of 2,2'-biindoles from 2-ethynylanilines.

[Cp*IrCl2]2 catalyzes the cyclization of 2-ethynylanilines to 2,2'-biindoles via intramolecular hydroamination. A reaction pathway has been proposed on the basis of deuterium labeling experiments and computational studies.

Facile synthesis of single crystalline rhenium (VI) trioxide nanocubes with high catalytic efficiency for photodegradation of methyl orange.

Single-crystalline rhenium trioxide (ReO3) nanocubes have been prepared for the first time without the need of surfactants via controlled reduction of rhenium (VII) oxide (Re2O7), sandwiched between silicon wafers at 250°C. The metallic ReO3 nanocubes are magnetic and possess surface plasmon resonance (SPR) bands down to the NIR region. The nanocubes also show very high catalytic activity toward the photodegradation of methyl orange (MO) under ambient conditions. A mechanism has been proposed to account for the photodegradation process.

Preparation of rhenium nanoparticles via pulsed-laser decomposition and catalytic studies.

Rhenium (Re) nanoparticles have been synthesized by pulsed-laser decomposition of ammonium perrhenate (NH(4)ReO(4)) or dirhenium decacarbonyl (Re(2)(CO)(10)) in the presence of 3-mercaptopropionic acid (MPA) as capping agent, in both aqueous and organic media. Preliminary studies showed that the MPA-capped Re nanoparticles are capable of catalyzing the isomerization of 10-undecen-1-ol to internal alkenols via long chain migration of the C=C double bond at ca. 200°C. A one-pot synthesis of graphite-coated Re nanoparticles has also been achieved by pulsed-laser decomposition of Re(2)(CO)(10), due to photo-induced catalytic graphitization of the phenyl groups of PPh(3) on the surface of rhenium nanoparticles.

Ligand substitution from the (eta5-DMP)Mn(CO)2(Solv) [DMP = 2,5-dimethylpyrrole, Solv = solvent] complexes: to ring slip or not to ring slip?

The mechanism and energetics of the displacement of solvent from photolytically generated (eta(5)-DMP)Mn(CO)(2)(Solv) complexes has been studied [DMP = 2,5-dimethylpyrrole, Solv = solvent]. Rate enhancement relative to the eta(5)-cyclopentadienyl (Cp) system is not observed in the displacement of weakly bound solvents. The bond dissociation enthalpies obtained from the kinetic analysis are in good agreement with the values obtained by detailed density functional theory (DFT) calculations. The results indicate that for both the Cp and the DMP based systems the displacement of weakly bound solvents proceeds by a dissociative or I(d) mechanism. This is in sharp contrast to CO displacement from (eta(5)-DMP)Mn(CO)(3), which is known to proceed by an associative mechanism by way of an eta(3) ring slip intermediate. The associative substitution pathway only becomes competitive with the dissociative channel when the Mn-Solv bond dissociation enthalpy is more than 33 kcal/mol.