1072
R. H. Meijer et al. / Tetrahedron 60 (2004) 1065–1072
4.1.13. Isolation of (Ph4C5O)Ru(CO)2PPh3 formed
during the dehydrogenation of 1-octanol. After the
dehydrogenation of 1-octanol according to the standard
procedure, the reaction mixture was allowed to cool to room
temperature overnight. A yellow solid had precipitated.
Removal of the mother liquor by filtration yielded a yellow
solid that was purified by column chromatography (silica
gel, CH2Cl2) and crystallized from CH2Cl2:hexane, the
The crystal structure work was supported by the Council for
the Chemical Sciences of the Netherlands Organization for
Scientific Research (CW-NWO).
References and notes
1
product was obtained as a few yellow crystals. H NMR
1. Sheldon, R. A.; van Santen, R. A. Catalytic oxidations:
principles and applications; World Scientific: Singapore,
1995; p 239.
(CDCl3): d¼7.44–6.94 (m, 35H); 13C NMR (CDCl3):
d¼202.2, 202.1, 133.5, 133.1, 133.0, 132.6, 132.6, 132.1,
131.2, 130.3, 130.1, 130.0, 128.2, 128.1, 127.6, 126.7,
125.9, 105.6, 105.5, 81.8; 31P NMR (CDCl3): d¼39.0; IR
(ATR): n¼3051, 2006, 1951, 1605, 1575, 1498, 1486, 1445,
1435, 1401, 1312, 1091, 1072, 1029, 1001, 838, 805, 757,
740, 727, 708, 690 cm21. MALDI-TOF m/z 777, 749, 805.
Rf¼0.22 (CH2Cl2). Mp 205 8C (dec.).
¨
2. Aranyos, A.; Csjernyik, G.; Szabo, K.; Backvall, J.-E. Chem.
Commun. 1999, 351.
3. (a) Wang, G.-Z.; Backvall, J.-E. J. Chem. Soc., Chem.
¨
Commun. 1992, 337. (b) Tomioka, H.; Takai, K.; Oshima,
K.; Nozaki, H. Tetrahedron Lett. 1981, 22, 1605.
4. Ito, T.; Horino, H.; Koshiro, Y.; Yamamoto, A. Bull. Chem.
Soc. Jpn 1982, 55, 504.
4.2. Crystals structure determination of
(Ph4C5O)Ru(CO)2PPh3
5. Menashe, N.; Shvo, Y. Organometallics 1991, 10, 3885.
6. Tolman, C. A. Chem. Rev. 1977, 77, 313.
7. Van Leeuwen, P. W. N. M.; Kamer, P. C. J.; Reek, J. N. H.
Pure Appl. Chem. 1999, 71, 1443.
A yellow crystal having approximate dimensions of
0.27£0.42£0.54 mm3 mounted on top of a glass capillary
was used for X-ray study. The data were collected on a
Nonius KappaCCD diffractometer. A correction for absorp-
tion was considered unnecessary. Reduced-cell calculations
did not indicate higher lattice symmetry. All data were
collected at 150 K using graphite-monochromated Mo Ka
8. Dierkes, P.; Van Leeuwen, P. W. N. M. J. Chem. Soc., Dalton
Trans. 1999, 1519.
9. Van der Veen, L. A.; Keeven, P. H.; Schoenmaker, G. C.;
Reek, J. N. H.; Kamer, P. C. J.; Van Leeuwen, P. W. N. M.;
Lutz, M.; Spek, A. L. Organometallics 2000, 19, 872.
10. Van Leeuwen, P. W. N. M.; Kamer, P. C. J.; Reek, J. N. H.
CATTECH 2000, 3, 164.
˚
radiation (l¼0.71073 A). The structure was solved by
automatic Patterson methods (DIRDIF99).18 The structure
was refined on F 2, using full-matrix least squares
techniques (SHELXL97).19 Neutral atom scattering factors
and anomalous dispersion corrections were taken from the
International Tables for Crystallography.20 Validation,
geometrical calculations and illustrations were performed
with PLATON.21
11. Chatt, J.; Shaw, B. L.; Field, A. E. J. Chem. Soc. 1964, 3466.
12. Beck, C. M.; Rathmill, S. E.; Jung Park, Y.; Chen, J.; Crabtree,
R. H. Organometallics 1999, 18, 5311.
13. Shirakawa, E.; Yoshida, H.; Takaya, H. Tetrahedron Lett.
1997, 38, 3759.
14. (a) Naota, T.; Takaya, H.; Murahashi, S.-I. Chem. Rev. 1998,
98, 2599. (b) Blum, Y.; Reshef, D.; Shvo, Y. Tetrahedron Lett.
1981, 22, 1541. (c) Shvo, Y.; Blum, Y.; Reshef, D.;
Maritmenzin, M. J. Organomet. Chem. 1982, 226, C21.
The crystal structure has been deposited at the Cambridge
Crystallographic Data Center as (h4-2,3,4,5-tetraphenyl-
2,4-cyclopentadien-1-one)-dicarbonyl-triphenylphosphine-
ruthenium(0) dichloromethane solvate and allocated the
deposition number CCDC 223319.
ˇ
15. Almeida, M. L. S.; Kocovsky, P.; Backvall, J.-E. J. Org.
¨
Chem. 1996, 61, 6587.
16. Shirakawa, E.; Yamasaki, K.; Hiyama, T. Synthesis 1998, 271.
`
17. Mouries, V.; Waschbu¨sch, R.; Carran, J.; Savignac, P.
Synthesis 1998, 1544.
18. Beurskens, P. T.; Admiraal, G.; Beurskens, G.; Bosman, W. P.;
´
Garcıa-Granda, S.; Gould, R. O.; Smits, J. M. M.; Smykalla, C.
Crystal data: C49H35O3PRu·CH2Cl2, M¼888.74, tetragonal,
space group I41=a (No. 88), a¼22.1040(1), c¼
3
˚
˚
33.2826(2) A, V¼16261.44(14) A , Z¼16, Dcalc¼1.452
The DIRDIF99 program system; Technical Report of the
Crystallography Laboratory, University of Nijmegen: The
Netherlands, 1999.
g cm23
,
m(Mo Ka)¼0.600 mm21
,
F(000)¼7264,
T¼150 K.
19. Sheldrick, G. M. SHELXL97, Program for crystal structure
¨
refinement; University of Gottingen, 1997.
Data collection and refinement: umin, umax¼1.8, 27.58, data
set (hkl-range)¼228:28, 228:28, 243:42, total
data¼123,055, total unique data¼9325 (Rint¼0.050),
number of refined parameters¼514, final R¼0.0312 [for
8043 I . 2sðIÞ], final wR2¼0.0803, goodness of fit¼1.03,
20. International tables for crystallography; Wilson, A. J. C., Ed.;
Kluwer Academic: Dordrecht, 1992; Vol. C.
21. Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7.
22. Yamazaki, S.; Taira, Z. J. Organomet. Chem. 1999, 578, 61.
23. A significant solvent effect has been observed for these
reactions. Apolar solvents such as p-xylene, decaline, polar
solvents like NMP, DMA and DMSO and polar protic solvents
like phenol and 3-ethyl-3-pentanol were studied. With phenol
the best results were obtained (48% yield, 64% selectivity at
100 8C, 1 h).
23
˚
min. and max. residual density¼20.86, 0.68e A
.
Acknowledgements
The authors gratefully acknowledge the support by the
Ministry of Economic Affairs as part of the Innovation
Oriented Research Program on Catalysis (IOP Catalysis).
¨
24. Kiplinger, J. L.; King, M. A.; Fechtenkotter, A.; Arif, A. M.;
Richmond, T. G. Organometallics 1996, 15, 5292.