M.J. Hanton et al. / Journal of Molecular Catalysis A: Chemical 346 (2011) 70–78
77
(ES +ve) m/z: 357 [N(CH2PPh2)3Ru]2+. Anal. Calcd. for C15H36NP3
4.2. General protocol for catalysis
(found): C, 63.98 (64.12); H, 4.85 (4.81); N, 1.82 (1.82).
A 50 mL s/s autoclave equipped with gas entraining stirrer and
sampling valve, was charged with Ru(acac)3, DMO, Zn and ligand,
then flushed with dry N2. Dry MeOH (30 mL) was added, and the
vessel was pressurised to 80 bar with H2 then vented, three times.
The vessel was then pressurised with 60 bar H2, heated to 100 ◦C
and when reaction temperature was attained, the vessel pressure
was topped up to 80 bar H2. This was considered to be the start-
ing point of reaction, an induction period normally being observed
between this point and the onset of catalysis. During reaction the
pressure in the vessel was maintained via a temperature com-
pensated ballast vessel and the rate of catalysis was assessed by
measuring the pressure drop in the ballast vessel which was logged
with a polling frequency of 1 s. Samples taken during catalysis via
the sampling valve were immediately analysed by GC–MS. When
gas uptake had ceased or the reaction was deemed to have run for
sufficient time, the vessel was cooled to RT, the excess pressure
vented, the vessel opened to air and a sample taken for GC–MS
analysis. Unless stated otherwise, a transparent solution free from
any precipitate was always observed upon opening the vessel. All
GC–MS data was response factor corrected based on calibration
experiments with compounds of interest. For the N-TriPhosEt lig-
and which is not air stable, the ligand was prepared as a stock
solution in MeOH and added to the vessel with the solvent, once an
inert atmosphere had been achieved.
Acknowledgements
MJH would like to thank Sasol Technology UK Ltd. and Sasol
Technology (Pty) Ltd for permission to publish this work. Prof.
David Cole-Hamilton, Prof. Bob Tooze and Dr. David Smith are
thanked for useful discussions. The referees are thanked for some
useful suggestions. PWM is grateful to the EPSRC for the award of
a Life Sciences Interface fellowship (EP/E039278/1).
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1
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]
(347 mg, 0.54 mmol) was added toluene (30 mL) and the mixture
brought to reflux. Evolution of CO gas was clearly observed on
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1
CH2). 31P { H} NMR (C6D6, 162 MHz): ı 8.25. FT-IR (/cm−1): car-
MeOH + DMO + Zn + TriPhosPh
DMO + Ru (acac)3).
;
MeOH + DMO + Zn + Ru(acac)3;
MeOH +
bonyl stretches 1940 (w), 1853 (w), others 1460 (s), 1376 (s). MS