Aryl-substituted organomolybdenum(II) complexes as olefin epoxidation catalysts

Lilian Graser; Robert M. Reich; Mirza Cokoja; Alexander Pöthig; Fritz E. Kühn

doi:10.1039/c5cy00447k

Aryl-substituted organomolybdenum(II) complexes as olefin epoxidation catalysts

Lilian Graser, Robert M. Reich, Mirza Cokoja, Alexander Pöthig, Fritz E. Kühn

Associate Professorship of Molecular Catalysis

Technical University of Munich

Research output: Contribution to journal › Article › peer-review

9 Scopus citations

Abstract

The epoxidation of selected olefins with a benzyl-substituted organomolybdenum complex and its fluorinated counterpart is described. With hexafluorobenzene (HFB) as solvent, turnover frequencies (TOFs) of >15500 h^-1 are achieved in the epoxidation of cyclooctene with tert-butyl hydroperoxide (TBHP) as the oxidant. The fluorinated complex, [CpMo(CO)₃BzF₅], proved to be superior to the non-fluorinated derivative in activity and selectivity with a variety of substrates. This can be explained via X-ray crystallography analysis and with the help of density functional theory (DFT) calculations. Besides, both compounds were applied in two-phase catalytic reactions. Recycling for multiple catalytic runs is achieved without a significant loss of activity.

Original language	English
Pages (from-to)	4772-4777
Number of pages	6
Journal	Catalysis Science and Technology
Volume	5
Issue number	10
DOIs	https://doi.org/10.1039/c5cy00447k
State	Published - 11 May 2015

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title = "Aryl-substituted organomolybdenum(II) complexes as olefin epoxidation catalysts",

abstract = "The epoxidation of selected olefins with a benzyl-substituted organomolybdenum complex and its fluorinated counterpart is described. With hexafluorobenzene (HFB) as solvent, turnover frequencies (TOFs) of >15500 h-1 are achieved in the epoxidation of cyclooctene with tert-butyl hydroperoxide (TBHP) as the oxidant. The fluorinated complex, [CpMo(CO)3BzF5], proved to be superior to the non-fluorinated derivative in activity and selectivity with a variety of substrates. This can be explained via X-ray crystallography analysis and with the help of density functional theory (DFT) calculations. Besides, both compounds were applied in two-phase catalytic reactions. Recycling for multiple catalytic runs is achieved without a significant loss of activity.",

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T1 - Aryl-substituted organomolybdenum(II) complexes as olefin epoxidation catalysts

AU - Graser, Lilian

AU - Reich, Robert M.

AU - Cokoja, Mirza

AU - Pöthig, Alexander

AU - Kühn, Fritz E.

PY - 2015/5/11

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N2 - The epoxidation of selected olefins with a benzyl-substituted organomolybdenum complex and its fluorinated counterpart is described. With hexafluorobenzene (HFB) as solvent, turnover frequencies (TOFs) of >15500 h-1 are achieved in the epoxidation of cyclooctene with tert-butyl hydroperoxide (TBHP) as the oxidant. The fluorinated complex, [CpMo(CO)3BzF5], proved to be superior to the non-fluorinated derivative in activity and selectivity with a variety of substrates. This can be explained via X-ray crystallography analysis and with the help of density functional theory (DFT) calculations. Besides, both compounds were applied in two-phase catalytic reactions. Recycling for multiple catalytic runs is achieved without a significant loss of activity.

AB - The epoxidation of selected olefins with a benzyl-substituted organomolybdenum complex and its fluorinated counterpart is described. With hexafluorobenzene (HFB) as solvent, turnover frequencies (TOFs) of >15500 h-1 are achieved in the epoxidation of cyclooctene with tert-butyl hydroperoxide (TBHP) as the oxidant. The fluorinated complex, [CpMo(CO)3BzF5], proved to be superior to the non-fluorinated derivative in activity and selectivity with a variety of substrates. This can be explained via X-ray crystallography analysis and with the help of density functional theory (DFT) calculations. Besides, both compounds were applied in two-phase catalytic reactions. Recycling for multiple catalytic runs is achieved without a significant loss of activity.

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Aryl-substituted organomolybdenum(II) complexes as olefin epoxidation catalysts

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