Polyethylene carboxylate-bound triruthenium clusters as alcohol oxidation catalysts

doi:10.1016/0923-1137(90)90079-J

Reactive Polymers

Volume 12, Issue 3, June 1990, Pages 291-295

Reactive Polymers

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Abstract

We have found that addition of polyethylene oligomers containing a terminal carboxylic acid group to solutions of [(CH₃CH₂CO₂)₆Ru₃O(H₂O)₃] ⁺CH₃CH₂CO₂⁻ allows us to recover quantitatively and reuse this ruthenium cluster as a catalyst for oxidation of primary and secondary alcohols with oxygen.

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Cited by (15)

Monomeric and extended oxo-centered triruthenium clusters
2001, Coordination Chemistry Reviews
The chemistry of μ-oxo-centered trinuclear ruthenium-carboxylate clusters, of general formula [Ru₃O(RCO₂)₆L₃]ⁿ, has been dealt with special emphasis on their spectroscopic and electrochemical properties, as well as their capability to form ligand-bridged oligomeric structures exhibiting pronounced electronic delocalization. Mixed systems containing trinuclear ruthenium clusters attached to transition metal complexes and porphyrins are also focused upon in this review article, from the point of view of cooperative interactions and supramolecular chemistry. The role of the trinuclear clusters as electron donor/acceptor groups, and their relevance in biomimetic systems, redox catalysis and molecular devices have been discussed.
The use of soluble polymers to effect homogeneous catalyst separation and reuse
1998, Catalysis Today
The use of soluble polymeric ligands for homogeneous catalysts separation is reviewed with emphasis on work from the author's laboratory. Examples discussed include polyethylene-bound catalysts, poly(alkene oxide)-bound catalysts, poly(N-isopropylacrylamide)-bound catalysts, fluorous polymer-bound catalysts and amphoteric polymer-bound catalysts. The utility of these systems is also discussed in the broader context of polymer-supported catalysis and the advantages and limitations of soluble polymeric ligands are discussed in this context.
Poly(maleic acid-co-styrene)-triruthenium cluster-catalysed oxidation of styrene with molecular oxygen
1994, Reactive Polymers
Silica-supported poly(maleic acid-co-styrene)-triruthenium clusters have been prepared by carboxyl exchange of (C₂H₅COO)₆Ru₃(μ₃O)(H₂O)₃⁺C₂H₅COO⁻ with carboxyl groups of silica-supported poly(maleic acid-co-styrene). The supported cluster displays a high activity in the oxidation of styrene under very mild conditions. The main product of the oxidation is benzaldehyde which results from the oxidative cleavage of styrene by molecular oxygen. During the catalytic reaction, the cluster on the support degrades most likely to monoruthenium species such as (£COO)₃Ru(V)O and £COO)₃Ru(III), and the pentavalent ruthenium species may be the catalytically active species in the oxidation. Therefore, the supported cluster could be recycled more than eight times without a noticeable decrease of its activity although it is already fragmented in the first cycle. A possible mechanism for the styrene cleavage is proposed.
Complexation of europium using polyethylene carboxylic acid
1993, Reactive Polymers
Competitive complexation of europium(III) carboxylates by an octadecanoic carboxylate and a terminally functionalized oligomeric ethylene carboxylate (M_n= ∼ 1500–2000) showed that there was little difference between a low molecular weight alkyl carboxylate ligand and an oligomeric polyethylene carboxylate ligand in their interaction with a metal salt in a toluene solution at 105°C. The most significant difference between these two carboxylate ligands was the facility with which the oligomeric carboxylate removes europium(III) from solution when the oligomer and octadecanoate were present at comparable concentrations. Comparison of calculations and experimental values for the amount of europium left in solution after equilibration of various ratios of terminally carboxylated oligomeric polyethylene and octadecanoic acids with europium(III) was used to evaluate the relative ligating ability of a soluble macromolecular and octadecyl carboxylate for europium(III) in toluene. Use of a less well-defined oxidized polyethylene instead of well-characterized terminally carboxylated oligomers as ligands had little effect on these equilibria. Experiments also showed that the solubility of these oligomerically ligated europium salts changed significantly over a temperature range of 60–85°C.
Transition metals in organic synthesis: Hydroformylation, reduction, and oxidation. Annual survey covering the year 1990
1992, Journal of Organometallic Chemistry
NewLigands
2012, Applied Homogeneous Catalysis with Organometallic Compounds: A Comprehensive Handbook in Three Volumes

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Polyethylene carboxylate-bound triruthenium clusters as alcohol oxidation catalysts

Abstract

Complete catalytic oxidation of volatile organics

Ind. Eng. Chem. Res.

Utilization of O2 for the specific oxidation of organic substrates with cobalt(II) catalysts

Coord. Chem. Rev.

Polymer-supported catalysts

Supported Metal Complexes

Hydrogen reduction of μ-3-oxo-triruthenium(III) acetate in dimethylformamide

Inorg. Chem.

The selective oxidation of primary alcohols to aldehydes by oxygen employing a trinuclear ruthenium carboxylate catalyst

J. Am. Chem. Soc.

Utilization of O₂ for the specific oxidation of organic substrates with cobalt(II) catalysts