Coordination Chemistry Reviews 248 (2004) 653–669
Review
Hydroformylation studies using high pressure NMR spectroscopy
Catherine Dwyer
∗
, Heidi Assumption, Johan Coetzee, Chantelle Crause,
Llewellyn Damoense, Megan Kirk
Sasol Technology Research & Development, P.O. Box 1, Sasolburg 1947, South Africa
Received 30 September 2003; accepted 15 January 2004
Available online 11 March 2004
Contents
Abstract ................................................................................................................................ 653
1. Introduction to HP-NMR spectroscopy ................................................................................................ 653
2. Hydroformylation with cobalt carbonyl-phosphine complexes............................................................................ 655
3. Experimental procedures ............................................................................................................. 656
4. Studies with limonene derived ligands ................................................................................................. 657
4.1. Reactivity of diastereomers..................................................................................................... 657
4.2. Catalyst preforming ...........................................................................................................
658
4.3. Effect of reaction parameters ...................................................................................................
658
4.4. Ligand starvation.............................................................................................................. 659
4.5. Formation of a disubsituted hydride ............................................................................................. 661
4.6. Effect of iron carbonyls ........................................................................................................ 662
4.7. Hydroformylation of 1-dodecene................................................................................................ 664
5. Studies with eicosyl phobane ......................................................................................................... 665
5.1. Catalyst preforming ........................................................................................................... 665
5.2. Ligand starvation.............................................................................................................. 665
6. Integration with other techniques ..................................................................................................... 667
7. Conclusions ........................................................................................................................ 668
Acknowledgements...................................................................................................................... 669
References ............................................................................................................................. 669
Abstract
High pressure nuclear magnetic resonance (HP-NMR) spectroscopy has become a useful tool for homogeneous catalysis research, both in
industry and academia. It is a “window” on catalysis at variable temperatures and elevated pressures, and allows the researcher unprecented
access to information on catalyst behaviour under process conditions. HP-NMR studies carried out on modified cobalt hydroformylation
catalysts are presented from an industrial perspective. The ligands of interest are bridged bicyclic phosphines derived from phobane and
(R)-(+)-limonene. Integration of HP-NMR with HP-IR, molecular modelling and bench experiments is also discussed.
R
Co; PR
3
H
2
/CO;
ROH
© 2004 Elsevier B.V. All rights reserved.
Keywords: Hydroformylation; High pressure NMR; Cobalt; Phosphabicyclononane
∗
Corresponding author. Tel.: +27-16-960-4443;
fax: +27-11-522-3593.
E-mail address: cathy.dwyer@sasol.com (C. Dwyer).
1. Introduction to HP-NMR spectroscopy
Understanding the mechanism of chemical reactions is
essential for the advancement of chemistry. This field was
traditionally the domain of academic researchers owing
to the significant time and effort required to gain this un-
0010-8545/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.ccr.2004.01.003