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Mechanistic aspects of dihydrogen activation and transfer during asymmetric hydrogenation in supercritical carbon dioxide
Author(s) -
Lange Susanne,
Brinkmann Axel,
Trautner Peter,
Woelk Klaus,
Bargon Joachim,
Leitner Walter
Publication year - 2000
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/(sici)1520-636x(2000)12:5/6<450::aid-chir26>3.0.co;2-h
Subject(s) - chemistry , catalysis , supercritical carbon dioxide , rhodium , deuterium , supercritical fluid , transfer hydrogenation , hexane , molecule , organic chemistry , hydrogen , photochemistry , ruthenium , physics , quantum mechanics
A new ”CO 2 ‐philic” chiral rhodium diphosphinite complex was synthesized and applied as catalyst precursor in the asymmetric hydrogenation of dimethyl itaconate in scCO 2 , scC 2 H 6 and various liquid organic solvents. Deuterium labeling studies and parahydrogen‐induced polarization (PHIP) NMR experiments were used to provide the first detailed mechanistic insight into the activation and transfer of the dihydrogen molecule during hydrogenation in scCO 2 . Chemical interactions between CO 2 and reactive intermediates of the catalytic pathway could be excluded as possible explanations for the experimentally verified difference in the catalytic behavior in scCO 2 and hexane. Chirality 12:450–457, 2000 © 2000 Wiley‐Liss, Inc.