4.1.4 Preparation of 6. The same procedure described for 3
is followed for the preparation of 6. Complex 1 (0.349 g, 0.346
mmol) and dichloro(1,5-cyclooctadiene)palladium (0.099 g,
0.346 mmol) with 20 cm3 of THF were taken in a 100 cm3 round
flask. The solution was frozen and degassed followed by filling
up with purified nitrogen. Then it was allowed to warm up to
25 ЊC and stirred for 2 h. Subsequently the resulting yellow-
ish brown solution was filtered through silica gel and purifi-
cation with centrifugal thin-layer chromatography (CTLC) was
and 20 cm3 of ether. Then, the water layer was extracted and
acidified with 20% HCl. After extraction again with ether (3 ×
30 cm3) the organic phase was collected and dried with
anhydrous MgSO4. The product was collected and measured
after filtration and concentration.
4.4 X-Ray crystallographic studies
Suitable crystals of 3, 4 and 6 were sealed in thin-walled glass
capillaries under nitrogen atmosphere and mounted on a
Bruker AXS SMART 1000 diffractometer. Intensity data were
collected in 1350 frames with increasing ω (width of 0.3Њ per
frame). The absorption correction was based on the symmetry
equivalent reflections using the SADABS program. The space
group determination was based on a check of the Laue sym-
metry and systematic absences, and was confirmed from the
structure solution. The structure was solved by direct methods
using a SHELXTL package.22 All non-H atoms were located
from successive Fourier maps and hydrogen atoms were refined
using a riding model. Anisotropic thermal parameters were
used for all non-H atoms and fixed isotropic parameters were
used for H atoms.23 Crystallographic data for 3, 4 and 6 are
summarized in Table 1.
carried out. The first pink band of the known compound
᎐
[{µ-P,P–PPh CH PPh }Co (CO) {µ-P(᎐O)Ph C᎐CP(᎐O)Ph }],
᎐
᎐
᎐
2
2
2
2
4
2
2
was eluted with CH2Cl2. The second yellow band of 6 was
eluted with CH2Cl2–MeOH (10 : 1). The solvent was removed in
vacuo and was identified as 6; 55% yield (0.225 g, 0.189 mmol).
Compound 6 can be obtained by an alternative route as
described below. Pd(OAc)2 (0.082 g, 0.367 mmol) and one
equivalent of 1 (0.371 g, 0.367 mmol) were dissolved in 20 cm3
of methanol and THF, respectively, in a 100 cm3 flask. The
solution was stirred at 25 ЊC for 45 min. Subsequently, 1 equiv-
alent of dry CoCl2 (0.080 g, 0.367 mmol) was added to the
solution under nitrogen and stirred at 25 ЊC for 2 h. The similar
separation procedure as above is followed for obtaining 6 and
the isolated yield is 50% (0.218 g, 0.184 mmol).
1
CCDC reference numbers 207225 (3), 207226 (4) and 197793
(6).
lographic data in CIF or other electronic format.
Yellow solid; H NMR (CD2Cl2, δ/ppm): 2.98 (t, 2H, CH2),
6.98–7.94 (m, 40H, arene); 13C NMR (CDCl3 δ/ppm): 36.13 (t,
1C, CH2), 128.65 (d, 8C, arene); 31P NMR (CD2Cl2 δ/ppm): 35.9
(2P of dppm), 48.9 (2P of dppa); IR (KBr): ν(CO) 2101, 2927
cmϪ1; Anal. Calc. for 6: C, 55.7; H, 3.57. Found: C, 54.52; H,
3.81%; MS (FAB): m/z 1151 (Mϩ Ϫ Cl); mp = 162–180 ЊC
(decomp.).
Acknowledgements
We thank the National Science Council of the R.O.C. (Grant
NSC-91–2113-M-005–017) for supporting this work.
4.2 General procedures for the Suzuki cross-coupling reactions
Suzuki cross-coupling reactions were performed according to
the following procedures.
References
Method a21 (conducted in a THF–H2O biphasic medium).
Complex 6 (0.012 mg, 0.010 mmol) and phenylboronic acid
(0.183 g, 1.500 mmol) were charged into a suitable oven-dried
Schlenk flask. The flask was evacuated and backfilled with
nitrogen before adding THF (5 mL), 3 M NaOH solution
(1 mL) and aryl halide (1.000 mmol). Note that solid aryl
halides were added prior to the evacuation/backfill cycle. The
flask was sealed with a Teflon screw cap and the solution was
stirred at 65 ЊC for 16 h. The mixed solution was extracted with
toluene (20 mL), dried with anhydrous magnesium sulfate,
filtered and concentrated in vacuo. The crude material was
purified by flash chromatography on silica gel.
1 (a) D. J. Elliot, D. G. Holah, A. N. Hughes, V. R. Magnuson, I. M.
Moser, R. J. Puddephatt and W. Xu, Organometallics, 1991, 10,
3933; (b) Applied Homogeneous Catalysis with Organometallic
Compounds, ed. B. Cornils and W. A. Herrmann, VCH, New York,
1996, vol. 1 and 2; (c) R. Noyori, Asymmetric Catalysis In Organic
Synthesis, John Wiley & Sons, Inc., New York, 1994; (d ) G. W.
Parshall and S. D. Ittel, Homogeneous Catalysis, John Wiley & Sons,
Inc., New York, 2nd edn., 1992, ch. 8; (e) K. P. C. Vollhardt, Acc.
Chem. Res., 1977, 10, 1; ( f ) H. B. Kagan, Asymmetric Synthesis
Using Organometallic Catalysts, in Comprehensive Organometallic
Chemistry, ed. G. Wilkinson, F. G. A. Stone and A. W. Abel,
Pergamon Press, Oxford, 1982, vol. 8, ch. 53; (g) Comprehensive
Asymmetric Catalysis, ed. E. N. Jacobsen, A. Pfaltz and H.
Yamamoto, Springer-Verlag, New York, 1999, vol. I.
2 (a) J. J. Bishop, A. Davidson, M. L. Katcher, D. W. Lichtenberg,
R. E. Merrill and J. C. Smart, J. Organomet. Chem., 1971, 27,
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Chem. Commun., 1989, 775; (c) A. K. Powell and M. J. Went,
J. Chem. Soc., Dalton Trans., 1992, 439; (d ) A. Slazer, Coord. Chem.
Rev., 2003, 242, 59.
3 F.-E. Hong, Y.-C. Chang, R.-E. Chang, S.-C. Chen and B.-T. Ko,
Organometallics, 2002, 21, 961.
4 F.-E. Hong, Y.-C. Huang, S.-L. Wang and F.-L. Liao, Inorg. Chem.
Commun., 1999, 2, 450.
5 (a) A. Suzuki, in Metal-Catalyzed Cross-coupling Reactions
ed. F. Diederich and P. J. Stang, Wiley-VCH, Weinheim, Germany,
1998, ch. 2; (b) N. Miyura and A. Suzuki, Chem. Rev., 1995, 95,
2457; (c) A. Suzuki, J. Organomet. Chem., 1999, 576, 147.
6 (a) A. F. Littke, C. Dai and G. C. Fu, J. Am. Chem. Soc., 2000, 122,
4020; (b) J. McNulty, A. Capretta, J. Wilson, J. Dyck, G. Adjabeng
and A. Robertson, Chem. Commun., 2002, 1986.
7 (a) M. R. Netherton, C. Dai, K. Neuschüta and G. C. Fu, J. Am.
Chem. Soc., 2001, 123, 10099; (b) J. H. Kirchhoff, M. R. Netherton,
I. D. Hills and G. C. Fu, J. Am. Chem. Soc., 2002, 124, 13662.
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VCH, New York, 1996, vol. 1.
Method b (conducted in a toluene medium). Complex 6
(0.012 mg, 0.010 mmol), the phenylboronic acid (0.183 g, 1.500
mmol) and K3PO4 (0.425 g, 2.000 mmol) were charged into a
suitable oven-dried Schlenk flask. The flask was evacuated and
backfilled with nitrogen before adding toluene (1 mL) and the
aryl halide (1.000 mmol) through a rubber septum. The mixture
was washed with aqueous NaOH (1 M, 20 mL) and the aque-
ous layer was extracted with ether (20 mL). The combined
organic layer was washed with brine (20 mL) and dried
with anhydrous magnesium sulfate, filtered, and concentrated
in vacuo. The crude material was purified by flash chromato-
graphy on silica gel.
4.3 General procedures for the catalytic carbonylation
reactions
1.5 mmol of aryl halide, 5 g of 60% KOH and 1 cm3 of CHCl3
were taken in a 100 cm3 round flask. and. The solution was
frozen and degassed, followed by filling up with purified nitro-
gen. Then, 0.075 mmol of 2 was added and the solution was
stirred at 25 ЊC for 24 h. The solution was then placed into a
separator funnel followed by adding 30 cm3 of degassed water
D a l t o n T r a n s . , 2 0 0 4 , 1 5 7 – 1 6 5
164
Hong, Fung-E
