Catalysts for the Hydroformylation of Olefins
FULL PAPERS
80.99 MHz, respectively with a spinning rate of 5.0–6.0 kHz
and a contact time of 2 ms. [MePþPh3]BrÀ was used as internal
standard. 29Si CP/MAS solid-state NMR spectra were also re-
corded on the same instrument operating at 39.75 MHz with
a spinning rate of 5.0–6.0 kHz with a contact time of 2 ms.
Fourier transform infrared spectra were obtained using a
Shimadzu FTIR-8400s spectrometer equipped with a Specac
Silver Gate (ZnSe crystal) single reflection attenuated total re-
flectance (ATR) system. Spectra were recorded from 600 cmÀ1
to 4000 cmÀ1 using a resolution of 4 cmÀ1 and 150 scans. Ther-
mogravimetric analysis (TGA) experiments were carried out
on a TA Instruments Q500 instrument under air flow
(100 mL minÀ1) at a uniform heating rate of 208C minÀ1
from 258C to 10008C. Approximately 10–20 mg of sample
were used for each experiment.
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Hydroformylation of 1-Octene (Scheme 4)
To a 300-mL stainless steel, stirred-tank Parr reactor equipped
with a pressure transducer and temperature control were add-
ed 50 mg of rhodium-containing catalyst (8.3 mmol Rh), cyclo-
hexane (90 mL), 1-octene (0.1 mol, 11.2 g) and m-xylene
(11.2 g) as the internal standard. The reactor was sealed and
flushed 3 times with carbon monoxide and then pressurized
to 500 psi with carbon monoxide. The reactor was then further
pressurized to 1000 psi with hydrogen to give a 1:1 ratio of CO/
H2 with a total pressure of 1000 psi. The reactor was stirred at
600 rpm at 708C. Samples were routinely withdrawn and ana-
lyzed by means of GC and NMR.
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Scheme 4. The hydroformylation reaction
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Acknowledgements
A. S. is a Canada Research Chair in Catalysis Using Nanostruc-
tured Materials. We thankthe Canada Foundation for Innova-
tion (CFI), the Natural Sciences and Engineering Research
Council (NSERC), and SASOLTechnology (R & D) for finan-
cial support of this work. We also thank Mike Green at SASOL
Technology for support, Tamer El Bokl for recording TGA
spectra, and Glenn Facey and Cheryl McDowall for recording
NMR spectra.
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