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Fluorinated Solvents in Methyltrioxorhenium‐Catalyzed Olefin Epoxidations
Author(s) -
Altmann Philipp,
Cokoja Mirza,
Kühn Fritz E.
Publication year - 2012
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201200120
Subject(s) - chemistry , catalysis , lewis acids and bases , epoxide , olefin fiber , decomposition , solvent , organic chemistry , polymer chemistry
Epoxidations with methyltrioxorhenium(VII) (MTO) as catalyst precursor and additives are examined in fluorinated solvents under various conditions. These fluorinated solvents have a strong influence on the 1 H NMR, 13 C NMR, and 17 O NMR spectroscopic data of the catalyst precursor, apparently contributing significantly to the catalytic activity of such systems. Accordingly, the highest turnover frequencies (TOF) obtained with MTO‐containing systems have been determined, reaching up to 39000 h –1 . Despite the high initial activity, such systems show a pronounced sensitivity to water leading also to faster catalyst decomposition. The high activity as well as the high sensitivity of the catalyst may be due to its solvent‐enhanced higher Lewis acidity, leading to quantitative epoxide yields only when quite stable epoxides are the end products and very high amounts of Lewis base additives are applied.