A Recoverable Ruthenium Aqua Complex Supported on Silica Particles: An Efficient Epoxidation Catalyst

Ferrer, Íngrid; Fontrodona, Xavier; Roig, Anna; Rodríguez, Montserrat; Romero, Isabel

doi:10.1002/chem.201604463

Cited by 15 publications

(10 citation statements)

References 58 publications

(68 reference statements)

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“…The sixth coordination site is occupied by the monodentate acetonitrile ligand. All bond distances and angles are within the expected values for these types of complexes. − For instance, it is interesting to note that the Ru–N2 bond length in the bpy ligand, where the N2 atom is placed trans to the pyridyl N4 atom of trpy, is longer (2.069 Å) than the analogous distance Ru–N1 (2.033 Å), where the N1 atom is trans to the N6 atom of the acetonitrile ligand. This evidence highlights the stronger trans influence of the pyridine ring with respect to the acetonitrile ligand.…”

Section: Results and Discussionsupporting

confidence: 56%

Aqueous Persistent Noncovalent Ion-Pair Cooperative Coupling in a Ruthenium Cobaltabis(dicarbollide) System as a Highly Efficient Photoredox Oxidation Catalyst

et al. 2021

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An original cooperative photoredox catalytic system, [RuII(trpy)(bpy)(H2O)][3,3′-Co(1,2-C2B9H11)2]2 (C4; trpy = terpyridine and bpy = bipyridine), has been synthesized. In this system, the photoredox metallacarborane catalyst [3,3′-Co(1,2-C2B9H11)2]− ([1]− ) and the oxidation catalyst [RuII(trpy)(bpy)(H2O)]2+ (C2′) are linked by noncovalent interactions and not through covalent bonds. The noncovalent interactions to a large degree persist even after water dissolution. This represents a step ahead in cooperativity avoiding costly covalent bonding. Recrystallization of C4 in acetonitrile leads to the substitution of water by the acetonitrile ligand and the formation of complex [RuII(trpy)(bpy)(CH3CN)][3,3′-Co(1,2-C2B9H11)2]2 (C5), structurally characterized. A significant electronic coupling between C2′ and [1]− was first sensed in electrochemical studies in water. The CoIV/III redox couple in water differed by 170 mV when [1]− had Na+ as a cation versus when the ruthenium complex was the cation. This cooperative system leads to an efficient catalyst for the photooxidation of alcohols in water, through a proton-coupled electron-transfer process. We have highlighted the capacity of C4 to perform as an excellent cooperative photoredox catalyst in the photooxidation of alcohols in water at room temperature under UV irradiation, using 0.005 mol % catalyst. A high turnover number (TON = 20000) has been observed. The hybrid system C4 displays a better catalytic performance than the separated mixtures of C2′ and Na[1], with the same concentrations and ratios of Ru/Co, proving the history relevance of the photocatalyst. Cooperative systems with this type of interaction have not been described and represent a step forward in getting cooperativity avoiding costly covalent bonding. A possible mechanism has been proposed.

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Section: Results and Discussionsupporting

confidence: 56%

Aqueous Persistent Noncovalent Ion-Pair Cooperative Coupling in a Ruthenium Cobaltabis(dicarbollide) System as a Highly Efficient Photoredox Oxidation Catalyst

et al. 2021

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“…In this sense, covalent grafting of homogeneous catalysts onto insoluble porous solid supports with high surface, such as mesoporous silica materials, − is a good approach where the catalyst can be recovered by simple filtration. Also, multifunctional systems like nano or micro core–shell magnetic particles are very attractive alternatives to obtain recyclable and efficient catalysts due to the combination of the unique magnetic properties of the core together with the possibility to further functionalize the surface, and they have been the subject of extensive research in biotechnology and catalysis areas. , The application of an external magnetic field enables the removal of the catalytic particles in a simple way. − To date, few examples of well-defined molecular ruthenium catalysts supported onto the previously mentioned supports have been described in the literature for the hydration of nitriles. − …”

Section: Introductionmentioning

confidence: 99%

A Heterogeneous Ruthenium dmso Complex Supported onto Silica Particles as a Recyclable Catalyst for the Efficient Hydration of Nitriles in Aqueous Medium

Manrique

Ferrer

et al. 2019

Inorg. Chem.

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In the present work, we describe an efficient method for the covalent anchoring of a Ru-dmso complex onto two types of supports: mesoporous silica particles (SP) and silica coated magnetic particles (MSNP). First, we have prepared and characterized the molecular complexes containing the bidentate pyridylpyrazole ligands pypz-Me and pypz-CH2COOEt, with the formula [RuIICl2(pypz-R)(dmso)2] (R = Me, 1; CH2COOEt, 2). Complex 2 was anchored onto the silica supports, yielding the heterogeneous systems SP@2 and MSNP@2 which were fully characterized by IR, UV–vis, SEM, TEM, TGA, and XPS techniques. Hydration of representative nitriles has been tested with the molecular complexes and their SP@2 and MSNP@2 heterogeneous counterparts, in aqueous medium under neutral conditions. The heterogeneous catalysts display high yields and excellent selectivity values. Both systems can be reused throughout several cycles for benzonitrile and acrylonitrile substrates, without any significant loss in reactivity. The MSNP@2 material can be easily recovered by a magnet, facilitating its reusability.

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“…The reaction at 40 °C with only 0.18 μmol L −1 ruthenium chloride and 0.06 μmol L −1 BSA‐HA leads to an epoxide yield of 78 % (TON=2613, TOF=109 h −1 ) after 24 h and a high enantiomeric excess of 82 % ee ( R ). This AME can compete with a recently reported ruthenium aqua complex supported on silica particles where an ee value of 79 % and a conversion of 92 % was found after 6 h for styrene at 25 °C using 1 mol % Ru . By increasing the MPR to 4 even a yield of 88 % can be achieved but the enantioselectivity decreases to 44 % ee ( R ).…”

Section: Resultsmentioning

confidence: 61%

Multicore Artificial Metalloenzymes Derived from Acylated Proteins as Catalysts for the Enantioselective Dihydroxylation and Epoxidation of Styrene Derivatives

Leurs

Dorn

Wilhelm

et al. 2018

Chemistry A European J

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Artificial metalloenzymes (AME's) are an interesting class of selective catalysts, where the chiral environment of proteins is used as chiral ligand for a catalytic metal. Commonly, the active site of an enzyme is modified with a catalytically active metal. Here we present an approach, where the commercial proteins lysozyme (LYS) and bovine serum albumin (BSA) can be converted into highly active and enantioselective AME's. This is achieved by acylation of the proteins primary amino groups, which affords the metal salts in the core of the protein. A series of differently acylated LYS and BSA were reacted with K OsO (OH) , RuCl , and Ti(OMe) , respectively, and the conjugates were tested for their catalytic activity in dihydroxylation and epoxidation of styrene and its derivatives. The best suited system for dihydroxylation is fully acetylated LYS conjugated with K OsO (OH) , which converts styrene to 1,2-phenylethanediol with an enantioselectivity of 95 % ee (S). BSA fully acylated with hexanoic acid and conjugated with three moles RuCl per mole protein shows the highest ee values for the conversion of styrene to the respective epoxide with enenatioselectivities of over 80 % ee (R), a TON of more than 2500 and a yield of up to 78 % within 24 h at 40 °C. LYS has two favored selective binding sites for the metal catalyst and BSA has even three. The AME's with titanate in the active center invert the enantioselectivity of styrene epoxidation.

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A Recoverable Ruthenium Aqua Complex Supported on Silica Particles: An Efficient Epoxidation Catalyst

Cited by 15 publications

References 58 publications

Aqueous Persistent Noncovalent Ion-Pair Cooperative Coupling in a Ruthenium Cobaltabis(dicarbollide) System as a Highly Efficient Photoredox Oxidation Catalyst

Aqueous Persistent Noncovalent Ion-Pair Cooperative Coupling in a Ruthenium Cobaltabis(dicarbollide) System as a Highly Efficient Photoredox Oxidation Catalyst

A Heterogeneous Ruthenium dmso Complex Supported onto Silica Particles as a Recyclable Catalyst for the Efficient Hydration of Nitriles in Aqueous Medium

Multicore Artificial Metalloenzymes Derived from Acylated Proteins as Catalysts for the Enantioselective Dihydroxylation and Epoxidation of Styrene Derivatives

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