Bimetallic cluster complexes: synthesis, structures and applications to catalysis

A brief history of the seminal discoveries in the field of bimetallic cluster complexes with their structures is presented. A review of some recent studies of palladium and platinum-ruthenium cluster complexes is concluded with a discussion of applications of these complexes in the area of homogeneous hydrogenation catalysis of alkynes.     

Ceria supported Ru~0-Ru~(δ+) clusters as efficient catalyst for arenes hydrogenation

Selective hydrogenation of aromatic amines,especially chemicals such as aniline and bis(4-aminocyclohexyl)methane for non-yellowing polyurethane,is of particular interests due to the extensive applications.To conquer the existing difficulties,in selective hydrogenation,,the Ru~0-Ru~(δ+)/CeO_2 catalyst with solid frustrated Lewis pairs was developed for aromatic amines hydrogenation with excellent activity and selectivity under relative milder conditions.The morphology,electronic and chemical properties,especially the Ru~O-Ru~(δ+) clusters and reducible ceria were characterized by X-ray diffraction(XRD),transmission electron microscopy(TEM),sca nning electronic microscopy(SEM),X-ray photoelectron sp ectroscopy(XPS),CO_2 tempe rature programmed deso rption(CO_2-TPD),H_2 tempe rature programmed reduction(H_2-TPR),H_2 diffuse reflectance Fourier transform infrared spectroscopy(H_2-DRIFT),Raman,etc.The 2% Ru/CeO_2 catalyst exhibited good conversion of 95% and selectivity greater than 99% toward cyclohexylamine.The volcano curve describing the activity and Ru state was found.Owning to the "acidic site isolation" by surrounding alkaline sites,condensation between the neighboring amine molecules could be effectively suppressed.The catalyst also showed good stability and applicability for other aromatic amines and heteroarenes containing different functional groups.     

Hydrogenation of β-N-substituted enaminoesters in the presence of ruthenium catalysts

β-Aminoesters were prepared in two simple steps from β-ketoesters derivatives and primary amines under mild conditions. Their hydrogenation was performed at 50 °C in the presence of several organometallic catalysts under acidic conditions. The new β-N-substituted aminoesters were isolated in moderate to good yields.     

Ligand manipulation and design for ruthenium metathesis and tandem metathesis-hydrogenation catalysis

Results of investigations into tandem ring-opening metathesis polymerization (ROMP)-hydrogenation are reviewed, in which hydrogen and 3-chloro-3-methyl-1-butyne provide simple chemical toggles to switch between metathesis and hydrogenation chemistry, enabling multiple tandem catalysis in chlorocarbon solvent. In the presence of methanol, hydrogenation of metathesis polymers can be carried out under 1 atm H₂. Issues of ligand design are examined in developing new Ru-diphosphine catalysts with improved selectivity, and an important decomposition pathway is identified for RuCl₂(PP)(CHR) systems (PP=chelating diphosphine).     

The importance of cluster fragmentation in the catalytic hydrogenation of phenylacetylene by PtRu5 carbonyl cluster complexes

has been shown to be a catalyst precursor for the hydrogenation of PhC₂H to styrene and ethylbenzene. Three new organometallic products have been found in the catalyst solutions. These are , , and Ru₅(CO)₁₁(μ₄-CCHCPh)(μ₄-HC₂Ph)(μ₃-HC₂Ph) (6). Compounds 4-6 have been synthesized independently and structurally characterized and each one has been tested independently for its ability to produce hydrogenation of PhC₂H catalytically. Compound 4 contains an open square-pyramidal cluster of five ruthenium atoms with one platinum atom bridging an edge of the cluster. It is structurally related to 2 but contains one less CO ligand and two hydrido ligands formed by the addition of one equivalent of hydrogen to the metal cluster. It can be obtained directly from 2 by reaction with hydrogen in the presence of trimethylamine oxide. Compound 5 is a tricoordinated mononuclear platinum complex containing one ligand, one CO ligand and one μ₂-PhC₂H ligand. Compound 5 can be obtained directly from by reaction with PhC₂H under an atmosphere of CO. Compound 6 was obtained from the reaction of Ru₅(CO)₁₅(μ₅-C) with PhC₂H in the presence of UV-Vis irradiation. Compound 6 contains three equivalents of PhC₂H; one is present as triply bridging PhC₂H ligand; one is a quadruply bridging ligand; the third one has formed a bond to the carbido ligand in the center of the metal cluster to form a novel tetra-metallated allyl ligand. Compound 5 has the highest catalytic activity of all three compounds and is believed to be responsible for the vast majority of the catalytic hydrogenation produced from the solutions of 2. Compound 4 is transformed into 5 under the conditions of catalysis.     

Synthesis, structure and hydrogenation catalytic activity of [Ru3(μ3,η-ampy)(μ,η:η-PhC=CHPh)(CO)6(PPh3) (Hampy = 2-amino-6-methylpyridine)

The compound [RU₃(μ₃,η²- -ampy)(μ₃η¹:η²-PhC=CHPh)(CO)₆(PPh₃)₂] (1) (ampy = 2-amino-6-methylpyridinate) has been prepared by reaction of [RU₃(η-H)(μ₃,η²- ampy) (μ,η¹:η²-PhC=CHPh)(CO)₇(PPh₃)] with triphenylphosphine at room temperature. However, the reaction of [RU₃(μ-H)(μ₃, η² -ampy)(CO)₇(PPh₃)₂] with diphenylacetylene requires a higher temperature (110°C) and does not give complex 1 but the phenyl derivative [RU₃(μ₃,η²-ampy)(μ,η ¹:η² -PhC=CHPh)(μ,-PPh₂)(Ph)(CO)₅(PPh₃)] (2). The thermolysis of complex 1 (110°C) also gives complex 2 quantitatively. Both 1 and 2 have been characterized by0 X-ray diffraction methods. Complex 1 is a catalyst precursor for the homogeneous hydrogenation of diphenylacetylene to a mixture of cis- and trans -stilbene under mild conditions (80°C, 1 atm. of H₂), although progressive deactivation of the catalytic species is observed. The dihydride [RU₃(μ-H)₂(μ ₃,η²-ampy)(μ,η¹:η²- PhC=CHPh)(CO)₅(PPh₃)₂] (3), which has been characterized spectroscopically, is an intermediate in the catalytic hydrogenation reaction.     

Searching for molecular arene hydrogenation catalysis in ionic liquids

Arene hydrogenation by homogeneous catalysts is a highly controversial area of research, with many of the mononuclear complexes shown to catalyse the reaction, being found to be pre-catalysts to nanoparticles, on closer examination. The solvent properties of ionic liquids, i.e., low nucleophilicity and high polarity, make them ideal, at least in principal, for homogeneous arene hydrogenation catalysts. In this paper, we described our attempts to prepare and study such systems, using either simple metal halides or ruthenium complexes including trinuclear ruthenium clusters as catalyst precursors.     

Base-promoted ruthenium carbonyl cluster complexes: From fundamental reactions to catalysis

An attempt to establish a link between the rich chemistry of ruthenium carbonyl clusters doped by nucleophilic anions, and the known effect of promoters in some ruthenium-based catalytic processes.     

Metal segregation in bimetallic clusters and its possible role in synergism and bifunctional catalysis

Aspects of the reactivity of segregated bimetallic compounds and their unusual catalytic properties are reviewed with an emphasis on the author's own studies of platinum—ruthenium mixed-metal cluster complexes and their ability to produce hydrogenation and hydrosilylation of alkynes, catalytically.     

Hydrogenation of cyclohexene catalyzed by ruthenium nitrosyl complexes: Crystal structures of catalyst precursors [CpRu(μ2-NO)2RuCp] and [CpRu(NO)(η-C6H10)] (Cp = η-C5(CH3)5)

Hydrogenation of cyclohexene with 0.1 mol% of the (nitrosyl)ruthenium catalyst [Cp^∗Ru(NO)(C₆H₅)₂] (1; Cp^∗ = η⁵-C₅(CH₃)₅) under 1.0 MPa of H₂ in water at 90 °C for 13 h afforded cyclohexane in 94% yield. The nitrosyl-bridged dinuclear complex [Cp^∗Ru(μ₂-NO)₂RuCp^∗] (2) and the mononuclear cyclohexene complex [Cp^∗Ru(NO)(η²-C₆H₁₀)] (3), which also serve as catalyst precursors, have been obtained from the reaction mixture. X-ray crystallographic analyses of 2 and 3 have revealed that the bridging nitrosyl ligands in 2 form an almost planar Ru₂N₂ four-membered ring with the Ru–Ru distance of 2.5366(5) Å, whereas the nitrosyl ligand in 3 is linear. On the other hand, a ruthenium complex without a nitrosyl ligand [Cp^∗Ru(CH₃CN)₃][OSO₂CF₃] proved to be less effective for this hydrogenation.     

Ionic liquids as acid/base buffers in non-aqueous solvents for homogeneous catalysis: A case of selective hydrogenation of olefins and unsaturated aldehyde catalyzed by ruthenium complexes

We present a novel approach to tune acidity/basicity in non-aqueous and low-water media by using a class of ionic liquids (ILs) with buffering characteristics, which was readily synthesized by the reaction of 1-alkyl-3-methylimidazolium hydroxide ([RMIM]OH) base moieties with a serials of binary or polybasic acids and defined as ionic liquid-buffers (IL-buffers). We have performed controlled experiments of hydrogenation of olefins and trans-cinnamaldehyde, catalyzed by [RuCl₂(PPh₃)₃] in non-aqueous media such as DMF and ILs in the presence of IL-buffers. Remarkable buffer dependence of the formation and catalytic behavior of ruthenium hydrides were evidenced by the kinetic studies and NMR measurements. The hydride [RuHCl(PPh₃)₃], being favorably formed in the presence of the IL-buffer with lower log₁₀([Base]/[Acid]), exhibited higher activity in the reduction of the CC bond against the carbonyl functionality of trans-cinnamaldehyde. While the hydride [RuH₄(PPh₃)₃], being preponderantly formed in the presence of the IL-buffer with higher log₁₀([Base]/[Acid]) showed activity and higher selectivity towards the CO reduction. Consequently, the hydrogenation performance of olefins and trans-cinnamaldehyde in non-aqueous system could be adjusted by adding the different IL-buffers. It is envisioned that the ability of IL-buffers to alter and precisely control the catalytic active species in non-aqueous or low-water systems might find appreciable applications for both fundamental studies and syntheses where the reactions are acid/base-sensitive.     

Irreversible cleavage of a carbene-rhodium bond in Rh-N-heterocyclic carbene complexes: implications for catalysis

Despite the generally accepted belief that carbene-metal bonds are strong and do not dissociate, the reaction of Rh-N-heterocyclic carbene complexes with triphenylphosphine in dichloroethane was determined to take place via cleavage of the Rh-carbene bond. The products of this reaction are Wilkinson’s catalyst and a bisimidazolium salt derived from reaction between dichloroethane and two equivalents of the carbene. The implications of this reaction for catalysis are significant since the carbene complex shows lower activity than Wilkinson’s catalyst in hydrogenation reactions. In non-halogenated solvents, the catalyst shows higher stability, such that the rate of exchange with free phosphine could be measured, and was determined to be ca. 10 times slower than in Wilkinson’s catalyst.     

Mechanism in homogeneous catalysis; NMR as a prime mover

An overview of the contribution of NMR to the development of our understanding of homogeneous catalysis is presented, with an emphasis on work from the author’s research group.     

Cobalt-Catalyzed Asymmetric Hydrogenation: Substrate Specificity and Mechanistic Variability

Asymmetric hydrogenation finds widespread application in academia and industry. And indeed, a number of processes have been implemented for the production of pharma and agro intermediates as well as flavors & fragrances. Although these processes are all based on the use of late transition metals as catalysts, there is an increasing interest in the use of base metal catalysis in view of their lower cost and the expected different substrate scope. Catalysts based on cobalt have already shown their potential in enantioselective hydrogenation chemistry. This review outlines the impressive progress made in recent years on cobalt-catalyzed asymmetric hydrogenation of different unsaturated substrates. We also illustrate the ligand dependent substrate specificity as well as the mechanistic variability in detail. This may well guide further catalyst development in this research area.     

Rhodium complexes with chiral counterions: achiral catalysts in chiral matrices

The neutral complexes [Rh(I)(NBD)((1S)-10-camphorsulfonate)] (2) and [Rh(I)((R)-N-acetylphenylalanate)] (4) reacted with bis-(diphenylphosphino)ethane (dppe) to form the cationic Rh(I)(NBD)(dppe) complexes, 5 and 6, respectively, accompanied by their corresponding chiral counteranions. Analogously, 4 reacted with 4,4^′-dimethylbipyridine to yield complex 7. Complexes 5 and 6 disproportionated in aprotic solvents to form the corresponding bis-diphosphine complexes 8 and 9, respectively. 8 was characterized by an X-ray crystal structure analysis. In order to form achiral Rh(I) complexes bearing chiral countercations new sulfonated monophosphines 13-16 with chiral ammonium cations were synthesized. Tris-triphenylphosphinosulfonic acid (H₃TPPS, 11) was used to protonate chiral amines to yield chiral ammonium phosphines 14-16. Thallium-tris-triphenylphosphinosulfonate (Tl₃TPPS, 12) underwent metathesis with a chiral quartenary ammonium iodide to yield the proton free chiral ammonium phosphine 13. Phosphines 15 and 16 reacted with [Rh(NBD)₂]BF₄ to afford the highly charged chiral zwitterionic complexes [Rh(NBD)(TPPS)₂][(R)-N,N-dimethyl-1-(naphtyl)ethylammonium]₅ (17) and [Rh(NBD)(TPPS)₂][BF₄][(R)-N,N-dimethyl-phenethylammonium]₆ (18), respectively. Complexes 5, 6, and 18 were tested as precatalysts for the hydrogenation of de-hydro-N-acetylphenylalanine (19) and methyl-(Z)-(α)-acetoamidocinnamate (MAC, 20) under homogeneous and heterogeneous (silica-supported and self-supported) conditions. None of the reactions was enantioselective.     

Synthesis of ruthenium/reduced graphene oxide composites and application for the selective hydrogenation of halonitroaromatics

Reduced graphene oxide （RGO） supported ruthenium （Ru） catalyst was prepared by an impregnation method using RuCI3 as a precursor and RGO as a support. The catalyst Ru/RGO was used for the selective hydrogenation ofp-chloronitrobenzene （p-CNB） to p-chloroaniline （p-CAN）, showing a selectivity of 96% at complete conversion of p-CNB at 60 ℃ and 3.0 MPa H2. The Ru/RGO catalyst was extremely active for the hydrogenation of a series of nitroarenes, which can be attributed to the small sized and the fine dispersity of the Ru nanoparticles on the RGO sheets characterized by TEM. Moreover, the catalyst also can be recycled five times without the loss of activity.     

Hydrogenation of conjugated CC and CO bonds: Quantum chemical preview before metal catalysis

Hydrogenation of acrolein, ethylene and formaldehyde by molecular hydrogen in gas phases, as a preview before metal catalysis, is investigated using density functional theory (PW91 and B3LYP), ab initio (MP2), and composite theoretical methods (G2, CBS-QB3, and CBS-APNO). Compared to the most accurate CBS-APNO method used in this paper, PW91 functional underestimates the barrier while B3LYP reproduces close results. All the reaction barriers are predicted to be no less than 70 kcal/mol and the CC hydrogenation is thermodynamically favored. Kinetically, however, the hydrogenation of CO bond is more favorable than that of the CC bond, especially for the isolated CO. The conjugation effect in acrolein greatly reduces the kinetic preference for the isolated CO hydrogenation. It is revealed that there is a good relationship between the energy barrier and the increase of the molecular H₂ bond length from the reactant to transition state.     

Ruthenium Nanoparticles Intercalated in Hectorite: A Reusable Hydrogenation Catalyst for Benzene and Toluene

The cationic organometallic aqua complexes formed by hydrolysis of [(C₆H₆)RuCl₂]₂ in water, mainly [(C₆H₆)Ru(H₂O)₃]²⁺, intercalate into sodium hectorite by ion exchange, replacing the sodium cations between the anionic silicate layers. The yellow hectorite thus obtained reacts in ethanol with molecular hydrogen (50 bar, 100°C) with decomposition of the organometallic aqua complexes to give a black material, in which ruthenium(0) nanoparticles (9–18 nm) are intercalated between the anionic silicate layers, the charges of which being balanced by hydronium cations. The black ruthenium-modified hectorite efficiently catalyses the hydrogenation of benzene and toluene in ethanol (50 bar H₂, 50°C), the turnover frequencies attaining 7000 catalytic cycles per hour. Dedicated to Professor Günter Schmid, pioneer of nanocluster chemistry, on the occasion of his 70th birthday