.mu.3-Oxo-triruthenium acetate cluster complexes as catalysts for olefin hydrogenation

Fouda, S A; Rempel, Garry L.

doi:10.1021/ic50191a001

Cited by 48 publications

(9 citation statements)

References 11 publications

(5 reference statements)

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The conversion of 10 into 6 is assumed to be irreversible. If it were reversible, complex 6 might provide entry to the cycle and would not be a catalytic intermediate [43].…”

Section: [Hru~(~-o)(~-ococh~)~(dmf)~]+(ococh~)-mentioning

confidence: 99%

Catalysis by Molecular Metal Clusters

Muetterties

Krause

1983

Angew. Chem. Int. Ed. Engl.

158

View full text Add to dashboard Cite

Dedicated to Professor Harald Schafer on the occasion of his 70th birthdayMolecular metal clusters form a very large and diverse family. They present the opportunity of modeling the intermediates involved in surface mediated catalytic reactions, of providing a source of very reactive mononuclear metal fragments, and of effecting catalytic cycles in which the cluster remains intact. The last mentioned aspect is the subject of this review article. The state-of-the-art of cluster catalysis is critically analyzed. The possibilities offered by molecular metal catalysts of performing catalytic reactions at multimetal atom sites are also discussed.

show abstract

“…The conversion of 10 into 6 is assumed to be irreversible. If it were reversible, complex 6 might provide entry to the cycle and would not be a catalytic intermediate [43].…”

Section: [Hru~(~-o)(~-ococh~)~(dmf)~]+(ococh~)-mentioning

confidence: 99%

Catalysis by Molecular Metal Clusters

Muetterties

Krause

1983

Angew. Chem. Int. Ed. Engl.

158

View full text Add to dashboard Cite

show abstract

“…Briey, based on previous studies, 19,20 coupled with the best-tted kinetic models, we suggest that in the rst step, only one metallic center -Ru 3+ (A)of complex 1 is reduced, while the other two are le to act as ligands. The A turns to Ru 0 and selfassemble to NPs from the nucleated size B. Ethanol serves as both solvent and reducing agent for Ru 3+ , and ethanol is oxidized in parallel.…”

Section: Introductionmentioning

confidence: 53%

Aggregation of catalytically active Ru nanoparticles to inactive bulk, monitored in situ during an allylic isomerization reaction. Influence of solvent, surfactant and stirring

Hitrik

Sasson

2018

RSC Adv.

View full text Add to dashboard Cite

The exploration of catalytic isomerization reactions of an allylic alcohol to ketone, in the presence of m-oxotriruthenium acetate as a precatalyst in alcohol solvents, has established that the catalyst is heterogeneous in nature and proceeds by means of the in situ formed Ru 0 nanoparticles (Ru 0 NPs). This reaction is used as an indicator for evaluating the kinetics and mechanism for metallic NP formation and self-assembly. In ethanol, complete conversion of the reactant is achieved under all experimental conditions tested.Conversely, in iso-propanol or n-pentanol the catalytic particles swiftly lose activity and the reaction arrests after partial conversion. We conclude that, in ethanol the process of NP self-assembly results in the formation of active and stable NPs of a specific size, named C-particles. Consequently, we propose an additional step for the established mechanism of NP self-assembly, namely the aggregation of C-NPs to inactive bulk-metal, labeled as D (C + C / D). D-particles differ from other NPs present in the catalytic cycle in size and in the catalytic activity. The effect of surfactant and mixing is also explored and the acquired observations strongly support the proposed mechanism of catalyst formation and decay.Addition of surfactants and/or mixing slowed down the reaction rate but dramatically improved the lifetime of the catalyst and the observed conversions. We attribute this phenomenon to the inhibition of the aggregation step of the active C-NPs to inactive D bulk-metal. The aggregation step of C-NPs to inactive D-bulk is assumed for the first time. This assumption prompts all the experimental data to be consistent. Introduction of the new kinetic step enables the use of the proposed mechanism with the reactions, where the catalyst loses its activity in the course of the reaction, and it converts the mechanism of the metal NP self-assembly into the more universal form. Scheme 1 The catalyst and the allylic isomerization reaction of interest. (A) The structure of m-oxo-triruthenium acetate (the complex), [Ru 3 O(OCOCH 3 ) 6 (H 2 O) 3 ][OCOCH 3 ]; (B) the isomerization reaction (reaction (1)) of 1-octene-3-ol to 3-octanone in the presence of the complex. Scheme 2 Mechanism 1: A -Ru-complex with 3 metal centers in its initial form -m-oxo-triruthenium acetate; Bnucleated small Ru 0 NP; Xremained Ru complex contains 2 Ru centers, obtained following the reduction of one of Ru centers in A; Clarger Ru 0 NP obtained from aggregation of at least 2B particles. a Reaction conditions: [reactant 1] 0 ¼ 2.6 (M) in the constant volume. The values are shown without corresponding errors in order to emphasize the trend.Scheme 4 The influence of Aliquat on the kinetics of the NPs selfassembly. The rationalization of the observed changes in the reaction (1) kinetic profiles in the presence of Aliquat: increase in conversion combined with slower rates.This journal is

show abstract

“…The solution was diluted with methanol and CSI-FT-ICR-MS was conducted in a positive ion mode (Fig. 22,23 In addition, inclusion of nitrosyl groups in such trinuclear ruthenium complexes has been observed. The starting Ru material, Ru(NO)(OAc) 3 (m/z = 309), disappeared and the peaks were widely distributed from m/z = 600 to 1600.…”

Section: Resultsmentioning

confidence: 99%

Solution processing of highly conductive ruthenium and ruthenium oxide thin films from ruthenium–amine complexes

Murakami

Hirose

et al. 2015

J. Mater. Chem. C

View full text Add to dashboard Cite

Highly conductive ruthenium metal (Ru 0 ) thin films and ruthenium oxide (RuO 2 ) films were prepared by a solution process. Solutions prepared from ruthenium(III) nitrosyl acetate and amines were spin-coated, and Ru 0 and RuO 2 thin films were formed after annealing in an inert atmosphere (nitrogen or vacuum) and oxygen, respectively. It was observed that amine-coordinated oxo-ruthenium clusters were formed in the precursor solution. The coordinated amines resulted in a change from oxidative decomposition to reductive decomposition of the ruthenium precursor under inert atmospheric conditions. The effects of different amine structures were compared, and alkanolamine and amino acids were found to produce Ru 0 films of higher quality (lower resistivity and higher surface flatness) than alkyl amines with primary amines being preferred to secondary and tertiary ones. These results were correlated with the structures of ruthenium complexes revealed by methods including high-energy X-ray diffraction with total correlation function and pair distribution function analyses. The resistivity values of Ru 0 and RuO 2 thin films prepared from ruthenium-alkanolamine complexes were 2.1 Â 10 À5 and 4.3 Â 10 À4 O cm, respectively, similar to those of vacuum-processed Ru 0 and RuO 2 ones. The Ru 0 film showed high stability against oxidation during further annealing in oxygen, even at nanometer-thickness (e.g., 25 nm).Technology (JAIST),

show abstract

.mu.3-Oxo-triruthenium acetate cluster complexes as catalysts for olefin hydrogenation

Cited by 48 publications

References 11 publications

Catalysis by Molecular Metal Clusters

Catalysis by Molecular Metal Clusters

Aggregation of catalytically active Ru nanoparticles to inactive bulk, monitored in situ during an allylic isomerization reaction. Influence of solvent, surfactant and stirring

Solution processing of highly conductive ruthenium and ruthenium oxide thin films from ruthenium–amine complexes

Contact Info

Product

Resources

About