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Organorhenium and Organomolybdenum Oxides as Heterogenised Catalysts

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Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 22))

Abstract

A variety of organomolybdenum and organorhenium complexes, most prominently methyltrioxorhenium(VII) (MTO), are applicable as efficient and selective oxidising agents in the presence of organic hydroperoxides (molybdenum complexes) or hydrogen peroxide (rhenium complexes). Besides strictly homogeneous oxidation catalysis, there is increasing interest in immobilizing homogeneous catalysts, both on carrier materials and in ionic liquids. Several methods that differ mainly in the anchoring mode and the nature of the supporting material have been described, and the resulting materials were applied to oxidation catalysis. Chiral oxidation catalysis with the compounds mentioned in the title is still in its infancy, but initial results point towards a promising future. The supported catalysts combine properties of homogeneous catalysts (reactivity, control and selectivity) and heterogeneous catalysts (enhanced stability and reusability). Homogeneous catalysts have a clearly defined composition, and mechanistic examinations are usually less problematic than with bulk (heterogeneous) catalysts, where the active sites are less clearly defined. It is also more straightforward to modify homogeneous catalysts by fine-tuning their ligand environments.

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Abbreviations

acac:

acetylacetonate

bpy:

2,2′-bipyridyl

Cp:

cyclopentadiene

dppa:

bis(diphenylphosphino)amine

Et:

ethyl

EXAFS:

extended X-ray absorption fine structure

IR:

infrared

MCM:

mobile crystalline material

Me:

methyl

MTO:

methyltrioxorhenium

NMR:

nuclear magnetic resonance

PBI:

polybenzimidazole

PEO:

polyethylene oxide

Ph:

phenyl

PPO:

polypropylene oxide

PS:

polystyrene

PSHPAMP:

polystyrene–divinylbenzene resin carrying an N-(2-hydroxypropyl)- 2-aminomethylpyridine ligand

PVP:

poly(4-vinylpyridine)

PVPN:

poly(4-vinylpyridine-N-oxide)

RT:

room temperature

RTIL:

room temperature ionic liquid

TBHP:

tert-butyl hydroperoxide

UHP:

urea hydroperoxide

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Acknowledgments

The authors are greatly indebted to the Fonds der Chemischen Industrie and to the Bayerische Forschungsstiftung (postdoctoral grant for C.F.) for financial support. M.A. Fredricks is acknowledged for helping to edit this work.

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Correspondence to Fritz E. Kühn .

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Franc Meyer Christian Limberg

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Freund, C., Herrmann, W., Kühn, F.E. (2006). Organorhenium and Organomolybdenum Oxides as Heterogenised Catalysts. In: Meyer, F., Limberg, C. (eds) Organometallic Oxidation Catalysis. Topics in Organometallic Chemistry, vol 22. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3418_029

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