G. Sánchez-Cabrera et al. / Journal of Organometallic Chemistry 694 (2009) 1949–1958
1957
(2 mL) and separated by preparative TLC plates using hexane/chlo-
roform (80:20) as eluent. The first band (bright yellow) was iden-
dimensions determination for compounds 3 and 5 were carried
out using the CAD EXPRESS software [26]. In the case of compound
4
tified as compound [Ru3(CO)8(
(3.8 mg, 18%), a second band (orange-yellow) contained com-
l
-H)2{
l
3-PCH2CH2P(C6F5)2}] (5)
4, data collection and cell dimensions determination and refine-
ment were carried out using Collect, Nonius BV, 1997–2000 and
the Otwinowski and Minor method [27].
pounds 2 and 3, a third yellow fraction corresponds to compound
[Ru3(CO)7(l-H)3(g
1-C6F5){
l
3-PCH2CH2P(C6F5)2}] (4) (1.1 mg, 5%).
A semi-empirical absorption correction method (SADABS) was ap-
plied in all cases. All non-hydrogen atoms were refined anisotrop-
ically. Hydrogen atoms in the methylene groups were fixed at
idealized positions and these were refined. Hydride groups were
observed in Fourier difference maps and their positions refined.
Crystals of 4 had to be cut to the appropriate size and this produced
microfractures which affected some structure factor values, thus
affecting the general refinement and the R value is relatively high.
All calculations were carried out using the SHELX-97 package [28].
The second band was separated again by preparative TLC using
hexane/chloroform (93:7) as eluent. After repeated chromatogra-
phy the mixture was separated into two bands, the second one
(yellow-orange) was identified as compound [Ru3(CO)9(
2-(C6F5)PCH2CH2P(C6F5)2}] (3) (10.2 mg, 40%) and the first band
(yellow) was identified as compound [Ru3(CO)8( -H)2(
1-C6F5)-
2-(C6F5)PCH2CH2P(C6F5)2}] (2) (5.0 mg, 17%).
A similar procedure was used to repeat the hydrogenation reac-
l-H)-
{
l
l
g
{
l
tion of [Ru3(CO)10{(C6F5)2P(CH2)2P(C6F5)2}] (1) (15 mg, 0.011
mmol) at 348 K increasing the reaction time to 30 min. The same
separation procedure yielded compounds, 5 (2.5 mg, 23%), 4
(0.9 mg, 7%), 3 (7.0 mg, 55%) and 2 (1.5 mg, 10%).
Analytical and spectroscopic data for compound 2: C34H6O8F19-
P2Ru3 (1287.5). Melting point: 147–149 °C. IR (cyclohexane):
5. Supplementary material
CCDC 706659, 705660 and 706661 contain the supplementary
crystallographic data for 3, 4 and 5. These data can be obtained free
of charge from The Cambridge Crystallographic Data Centre via
m
(CO) 2114(m), 2078(w), 2062(vs), 2056(m), 2044(s), 2038(s),
2016(w), 1990(m), 1966(w), 1942(w) cmꢀ1. Mass spectrometry
FAB: m/z (relative intensity): 1258 (15) (MꢀH,CO)+, 1202.5 (68),
1174.5 (43), 1146.5 (100), 1118.6 (34), 1089.7 (35). NMR data:
Acknowledgments
1H: 3.12(dddd) (1H) (CH2A), 2J
¼ 44:5, 3J
¼ 14:9,
1H—31PA
¼ 5:5; (CH2A), 2J
1H—31PB
¼ 44:5, 2J
We thank Ana Lilia Carrasco for obtaining the elemental analy-
ses, Víctor González, Guillermo Uribe and Ma. Luisa Rodríguez for
their assistance in obtaining NMR spectra, and Géiser Cuéllar for
obtaining the mass spectra. We express our gratitude to Dr. David
Watkins for his help in the refinement of the crystal structure of
compound 2. We are also grateful to the Consejo Superior de Inves-
tigaciones Científicas de España for the award of a licence of the
Cambridge Crystallographic Data Base. G.S.C., M.H.C. and F.Z.C.
thank CONACYT for the award of scholarships.
2J
¼ 14:9, 3J
¼
1H—1
H
1H—1
¼ 14:9, 3J
H
1H—31PA
1H—1H
14:9, 2J
¼ 5:5; ꢀ16.29 (ddm) (1H) (H1)
1H—1
H
1H—1H
2J
¼ 24:7, 3J
¼ 11:0; ꢀ18.80 (br) (H2) 2J
¼ 8:3.
1H—31PA
1H—31PB
1H—31PA
31P: 96.1 (s) (PA), 46.9 (s) (PB).
It was not possible to get appropriate elemental analyses for
this compound because it converts to compound 3.
Analytical and spectroscopic data for compound 3: C29H5O9F15-
P2Ru3 (1147.5): Microanalysis: Calc.: C, 30.36; H, 0.44. Expt.: C,
30.13; H, 0.30. Melting point: 135–138 °C. Mass spectrometry:
ESI m/z of the most intense peak in the isotopic pattern: 1149. IR
(cyclohexane):
m(CO) 2092(s), 2052(vs), 2038(s), 2028(sh),
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4.4. X-ray structural determination
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All crystals were mounted on glass fibers. Crystal data and details
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