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The best system (without any addition of a ligand) was a solu-
tion of nanoparticles derived from Rh(acac)(CO)2 in DMF, with a
yield of 97% aldehyde and a relatively high n/iso ratio of 70:30 in
comparison with the use of the rhodium complex Rh(acac)(CO)2,
as homogeneous catalyst, with a n/iso ratio of 45:55.
Furthermore, for the first time, catalyst recycling of nanoparti-
cles in a hydroformylation reaction using a TMS system was
shown.
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Acknowledgments
14. Lux, A., Dissertation, TU Dortmund (in preparation), 2012.
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285, 20–28; (b) Behr, A.; Henze, G.; Obst, D.; Turkowski, B. Green Chem. 2005, 7,
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16. The nanoparticles were synthesised by dissolving the rhodium precursor into
the polar solvent with stirring for 2 h at 80 °C and 20 bar hydrogen pressure.
All experiments were carried out under argon atmosphere. Chemicals were
purchased from VWR, Acros Organics and Messer Industriegase. The rhodium
The authors thank Umicore AG & Co. KG (Germany) for donating
the catalyst precursors. We acknowledge Iris Henkel for ICP-OES
measurements, Monika Meuris (Group of Professor Tiller) for
TEM measurements and Jens Beneken (Group of Professor Rehage)
for supporting the DLS measurements. These investigations were
carried out in the framework of the ‘Sonderforschungsbereich
Transregio 63’ supported by the Deutsche Forschungsgemeinschaft
(DFG).
precursor was received as
a donation from Umicore. Rhodium particle
synthesis and recycling in the TMS system were performed in a 300 mL
stainless steel Parr autoclave.
References and notes
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a 10 mL self-developed
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a
hydroformylation experiment, 1-dodecene (1.14 g, 6.8 Â 10À3 mol) was
dissolved in the rhodium nanoparticle solution prepared from the rhodium
precursor Rh(acac)(CO)2 (6.8 Â 10À6 mol, metal/substrate ratio = 1:1000) and
the polar solvent DMF (8.5 mL). In the recycling experiments, the non-polar
solvent n-decane was added to create the TMS system (50 wt % polar and
50 wt % non-polar solvent). The vessel was closed and the reaction solution
was placed in the reactor under an inert gas atmosphere. The pressure of the
synthesis gas was adjusted to 20 bar or 30 bar, respectively. The stirrer was
adjusted to 650 rpm in the multiplex or 800 rpm in the 300 mL autoclave. The
autoclave was heated to 110 °C. After the reaction time, the reactor was cooled
to room temperature within a few minutes by cooling with an ice bath. The
reactor was depressurized and flushed with argon. In the recycling
experiments, the catalyst phase was separated and used in the next reaction.
The reaction solutions were analyzed with a gas chromatograph (Hewlett-
Packard) equipped with a capillary column (HP 5) and a FID detector. 1-
Decanol was used as internal standard.
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