Aldehyde Olefination
1852 1859
up to ꢁ5000 collisions in the octopole; in the 24-pole, the number of
collisions was considerably higher. Moreover, the initial kinetic energy of
the ions was lost in the first several collisions. Although there was no
applied longitudinal electric field, the continuous ion current into either ion
guide created, by way of space-charge effects, a slight potential that drives
the ions through. Otherwise, the procedure closely resembled that in
previous publications. One concludes that the ions react under quasi-
thermal conditions at the 708C manifold temperature.
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Solution-phase NMR experiments were performed in a Varian Mercu-
ry 300 spectrometer operating at 121 MHz (for 31P) on solutions prepared
from [D8]THF (0.7 mL), benzaldehyde (10 mg), triphenylphosphine
(30 mg), ethyl diazoacetate (10 mg), and [ReO3(bipy)] [ReO4]À (4 mg)
(1.0:1.2:0.9:0.07 mole ratio for the reagents). Under these conditions, four
major species were observed in the 31P NMR spectrum: the phosphine,
phosphine oxide, and the cis and trans isomers of the phosphorane.
Chemical shifts for the species were reported by Woo.[5] Very small signals
(ꢂ5% total integration) were seen for other species. Control experiment
for olefin trans/cis ratio directly using commercially available ylide
(carbethoxymethylene triphenylphosphorane, Ph3P CHCO2Et) with benz-
aldehyde was also done in an NMR tube. In-situ NMR measurement
indicated that the reaction was finished in 24 hours at room temperature,
and trans/cis ratio of product was about 20/1. Another experiment with the
[Re2O7(bipy)] (3%)/PPh3 (3%)/P(OMe)3 (1.1 mmol)/PhCHO (1.0 mmol)/
EDA (1.5 mmol) system yielded 10% of the olefin with a trans/cis ratio of
2/1.
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Density functional theory (DFT) calculations were done by using the Titan
program package[23] running on a 1.2 GHz Athlon computer. All structures
were fully optimized by using the B3LYP method with the LACVP** basis
set. The LACVP** basis sets treat the 4s, 4p, and 4d, as well as the 3s and
3p, orbitals on ruthenium explicitly with a double-z basis; the inner
electrons were treated with an effective core potential. It used 6-31G** for
non-transition metal elements.
Acknowledgement
This work was supported by the Swiss National Science Foundation, the
ETHResearch Commission, and the Robert Gnehm Foundation. Helpful
discussions with Professor Erick Carreira (ETHZ¸rich) are acknowledged.
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bulk metal. Data from Engelhard Corp. give, as average for Rh, Ru,
and Re ingots in 2001, $42300, $3460, and $1250 per kg, respectively.
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[23] Titan 1.0.7, Schrˆdinger, 1500 SW First Ave., Suite 1180, Portland OR,
and Wavefunction, 18401 Von Karman Ave., Suite 370, Irvine CA.
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Received: May 17, 2002
Revised December 20, 2002 [F4103]
Chem. Eur. J. 2003, 9, No. 8
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