Mechanistic Aspects of Dihydrogen Activation and Transfer During Asymmetric Hydrogenation in Supercritical Carbon Dioxide

Author

Susanne Lange
Axel Brinkmann
Peter Trautner
Klaus Woelk, Missouri University of Science and TechnologyFollow
Joachim Bargon
Walter Leitner

Abstract

A new 'CO₂-philic' chiral rhodium diphosphinite complex was synthesized and applied as catalyst precursor in the asymmetric hydrogenation of dimethyl itaconate in scCO₂, scC₂H₆ 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 scCO₂. Chemical interactions between CO₂ and reactive intermediates of the catalytic pathway could be excluded as possible explanations for the experimentally verified difference in the catalytic behavior in scCO₂ and hexane.

Recommended Citation

S. Lange et al., "Mechanistic Aspects of Dihydrogen Activation and Transfer During Asymmetric Hydrogenation in Supercritical Carbon Dioxide," Chirality, vol. 12, no. 5-6, pp. 450 - 457, Wiley-Blackwell, May 2000.

The definitive version is available at https://doi.org/10.1002/(SICI)1520-636X(2000)12:5/6<450

Department(s)

Chemistry

International Standard Serial Number (ISSN)

0899-0042

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2000 Wiley-Blackwell, All rights reserved.

Publication Date

01 May 2000