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Trigonal‐Bipyramidal Lewis Base Adducts of Methyltrioxorhenium( VII ) and Their Bisperoxo Congeners: Characterization, Application in Catalytic Epoxidation, and Density Functional Mechanistic Study
Author(s) -
Kühn Fritz E.,
Santos Ana M.,
Roesky Peter W.,
Herdtweck Eberhardt,
Scherer Wolfgang,
Gisdakis Philip,
Yudanov Ilya V.,
Di Valentin Cristiana,
Rösch Notker
Publication year - 1999
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/(sici)1521-3765(19991203)5:12<3603::aid-chem3603>3.0.co;2-w
Subject(s) - adduct , trigonal bipyramidal molecular geometry , catalysis , chemistry , pyridine , lewis acids and bases , olefin fiber , base (topology) , density functional theory , pyrazole , medicinal chemistry , computational chemistry , crystallography , organic chemistry , crystal structure , mathematical analysis , mathematics
Pyrazole and pyridine adducts of methyltrioxorhenium( VII ) form bisperoxo complexes with excess H 2 O 2 (see picture). Density functional calculations reveal that the increased efficiency of these complexes as catalysts for olefin epoxidation originates from their stability and from the moderate energies of the corresponding transition states. Nonaromatic nitrogen‐base ligands reduce the catalytic performance of the adducts, in agreement with the computational results.