6052 Organometallics, Vol. 28, No. 20, 2009
Jung et al.
were dissolved in 2.5 mL of THF separately in 50 mL flasks.
Then, these two solutions were mixed and stirred at 25 °C for
1.5 h. A colorless oily product, chloro(diethylamino)phe-
nylphosphine, resulted.
3.4. Synthesis and Characterization of 8. In a N2-flashed
100 mL round-bottomed flask, 0.290 g (0.100 mmol) of 7bM
and 0.285 g (0.10 mmol) of Pd(COD)Cl2 were placed with 8 mL
of CH2Cl2. The solution was kept stirring at 60 °C for 1 h before
the solvent was removed under reduced pressure, and the residue
was separated by CTLC. A red-colored band was eluted using
a mixed solvent mobile phase (EA/CH2Cl2 = 10:1) and was
identified as [(7b0M)(7b0M-Hþ)Pd( μ-Cl)]2, 8. The yield of 8 is
86% (0.064 g, 0.043 mmol).
At 0 °C, chloro(diethylamino)phenylphosphine was added to
the solution of 1,10-dilithioferrocene, in 10 mL of THF. The
solution was allowed to warm to 25 °C and stirred for another
5 h. Subsequently, the solvent was removed under reduced
pressure and the residue was separated by CTLC. A dark yellow
colored band was eluted using a mixed solvent mobile phase
(MeOH/CH2Cl2 = 1:6) and was identified as (η5-C5H4-P(dO)-
(Ph)(H))2Fe, 7aB. The yield of 7aB is 68.4% (0.594 g, 1.37
mmol).
Selected Spectroscopic Data for 8. 1H NMR (CDCl3, δ/ppm):
1.10 (d, JP-H = 14.8 Hz, 36 H), 4.76 (s, 20 H), 4.40-4.65 (m,
16 H). 13C NMR (CDCl3, δ/ppm): 72.8 (s, 20 C, Cp), 70.6, 70.1,
69.1 (t, 20 C, Cp), 41.2, 41.0, 40.7 (t, 12 C, -C(CH3)3), 27.1 (s, 4
C, -C(CH3)3). 31P NMR (CDCl3, δ/ppm): 108.1. MS (FAB):
m/z=1442 (M - tBu - OH)þ. Anal. Calcd: C, 46.64; H, 5.17.
Found: C, 45.86; H, 5.24.
1
Selected Spectroscopic Data for 7aB. H NMR (CDCl3, δ/
ppm): 4.49-4.83 (m, 8 H, (η5-C5H4)2), 7.47-7.73 (m, 10 H, Ph),
7.92, 8.02 (d, 2 H, P-H, JP-H = 487.3, 489.3 Hz). 13C NMR
(CDCl3, δ/ppm): 72.5-73.3 (m, 10 C, (η5-C5H4)2), 128.6-132.1
(m, 12 C, Ph). 31P NMR (CDCl3, δ/ppm): 19.2 (d, 2 P, P-H,
3.5. Synthesis and Characterization of 9. In a N2-flashed
100 mL round-bottomed flask, 0.290 g (0.10 mmol) of 7bM
and 0.224 g (0.10 mmol) of Pd(OAc)2 were placed with 8 mL of
THF. The solution was kept stirring at 60 °C for 1 h before the
solvent was removed under reduced pressure, and the residue
was separated by CTLC. A red-colored band was eluted using
a mixed solvent mobile phase (EA/CH2Cl2 = 20:1) and was
identified as [(7b0M)(7b0M-Hþ)Pd(OAc)], 9.
J
P-H = 489.4 Hz). MS (FAB): m/z = 432 (Mþ). Anal. Calcd: C,
60.86; H, 4.64. Found: C, 59.50; H, 4.44.
3.3. Synthesis and Characterization of 7aM, 7bM, and 7cM. A
100 mL round-bottomed flask charged with a magnetic stir bar
was placed with 4.00 mmol of ferrocene (0.372 g) and 10 mL of
THF. The solution was kept stirring at 0 °C while 4.4 equiv of
1.9 mL of t-BuLi (2.3 M in penteane, 4.4 mmol) was slowly
added. After 1.0 h the solution was allowed to warm to 25 °C and
stirred for another 3 h. A dark red solid, 1,10-dilithioferrocene,
was obtained after the removal of solvent under reduced
pressure.
Selected Spectroscopic Data for 9. 1H NMR (CDCl3, δ/ppm):
1.28 (d, JP-H = 16.8 Hz, 9 H), 1.18 (d, JP-H=17.2 Hz, 9 H), 2.05
(s, 3 H), 4.16-4.58 (m, 18 H). 13C NMR (CDCl3, δ/ppm):
72.4 (s, 10 C, Cp), 70.6, 69.9, 67.8 (t, 10 C, Cp), 39.9, 39.3, 38.7 (t,
6
C, -C(CH3)3), 26.9-24.1 (m, 2
C, -C(CH3)3). 31P
First, 2.00 mol of tert-butyldichlorophosphine was dissolved
in 2.5 mL of THF. Then it was added to the solution of 1,10-
dilithioferrocene at 25 °C. The solution was allowed to warm to
room temperature and stirred for another 12 h at 60 °C.
Subsequently, the solution was allowed to cool to room tem-
perature, and a small amount of water was added to quench the
reaction. The organic portion was collected from the separatory
funnel after washing with ethyl acetate several times. Then, the
solvent was removed under reduced pressure, and the residue
was separated by CTLC. A dark yellow colored band was
eluted using a mixed solvent mobile phase (EA/CH2Cl2 = 3:1)
and was identified as (η5-C5H4-P(dO)(Ph)(H))2Fe, 7bM. The
same procedures were executed for the preparations of 7aM and
7cM except the starting materials were dichlorophenylpho-
sphine and dichlorocyclohexylphosphine, respectively. The
yields of 7aM, 7bM, and 7cM were 34% (0.210 g, 0.68 mmol),
64% (0.185 g, 1.28 mmol), and 46% (0.290 g, 0.92 mmol),
respectively.
NMR (toluene-d6, δ/ppm): 104.0, 105.5. MS (FAB): m/z=685
(M - CH3COO)þ.
3.6. General Procedures for the Suzuki-Miyaura Cross-
Coupling Reactions. Suzuki-Miyaura cross-coupling reactions
were performed according to the following procedures. Reac-
tants including 7aB (8.78 mg, 0.01 mmol), phenylboronic acid
(0.183 g, 1.50 mmol), and NaOH (0.120 g, 3.00 mmol) were
placed into a 20 mL Schlenk flask. The flask was evacuated and
backfilled with nitrogen before adding toluene (1.0 mL) and
2-bromothiophene (0.11 mL, 1.00 mmol). The solution was
stirred at 40 °C for 3 h. Subsequently, an excess amount of
water was added and the product was extracted with ether (3 ꢀ
20 mL). The combined organic extracts were dried over anhy-
drous MgSO4 and concentrated under vacuum. The crude
residue was purified by flash chromatography on silica gel.
Similar procedures are applied to the case of 7aM.
3.7. X-ray Crystallographic Studies. Suitable crystals of 7aB,
7aM, 7bM, 8, and 9 were sealed in thin-walled glass capillaries
under a nitrogen atmosphere and mounted on a Bruker AXS
SMART 1000 diffractometer. Intensity data were collected in
1350 frames with increasing ω (width of 0.3° 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 symmetry
and systematic absences and was confirmed using the structure
solution. The structure was solved by direct methods using the
SHELXTL package.15 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.16 Crystallographic data for compounds 7aB, 7aM,
7bM, 8, and 9 are available from the Supporting Information.
1
Selected Spectroscopic Data for 7aM. H NMR (CDCl3, δ/
ppm): 4.33 (s, 5 H, η5-C5H5), 4.44-4.48 (m, 4 H, η5-C5H4),
7.48-7.76 (m, 5 H, Ph), 8.03 (d, 1 H, P-H, JP-H = 483.3 Hz).
13C NMR (CDCl3, δ/ppm): 69.6 (s, 5 C, Cp), 70.4-71.9 (m, 5 C,
Cp), 128.5-132.1 (m, 6 C, Ph). 31P NMR (CDCl3, δ/ppm): 19.8
(d, 1 P, P-H, JP-H = 484.5 Hz). MS (FAB): m/z = 310 (Mþ).
Anal. Calcd: C, 61.97; H, 4.88. Found: C, 60.33; H, 5.63.
1
Selected Spectroscopic Data for 7bM. H NMR (CDCl3, δ/
ppm): 1.10 (d, JP-H = 16.8 Hz, 9 H), 4.36 (s, 5 H), 4.27-4.62 (m,
4 H), 6.88 (d, JP-H=454.5 Hz, 1 H). 13C NMR (CDCl3, δ/ppm):
23.2, 32.6 (d, JP-C = 71.1 Hz), 67.6(d, JP-C=110.1 Hz), 70.31,
71.2 (d, JP-C = 37.5 Hz), 72.2 (d, JP-C=33.1 Hz). 31P NMR
(CDCl3, δ/ppm): 47.5(s). (d, 1 P, P-H, JP-H = 454.0 Hz). MS
(FAB): m/z = 290 (Mþ). Anal. Calcd.: C, 57.96; H, 6.60. Found:
C, 56.84; H, 6.65.
1
Acknowledgment. We thank the National Science
Council of the ROC (grant NSC 95-2113-M-005-015-
MY3) for financial support.
Selected Spectroscopic Data for 7cM. H NMR (CDCl3, δ/
ppm): 1.21 (d, 4 H), 1.67 (m, 6 H), 4.36 (s, 5 H), 4.13-4.62 (m, 4
H), 7.06 (d, JP-H = 458.5 Hz, 1 H). 13C NMR (CDCl3, δ/ppm):
25.0 (d, JP-C = 9.1 Hz), 25.9 (d, JP-C = 15.2 Hz), 39.4 (d, JP-C
= 72.6 Hz), 68.3 (d, JP-C = 103.8 Hz), 69.6, 71.3 (d, JP-C
=
(15) Sheldrick, G. M. SHELXTL PLUS User’s Manual, Revision 4.1 ;
Nicolet XRD Corporation: Madison, WI, 1991.
(16) The hydrogen atoms were riding on carbons or oxygens in their
10.9 Hz), 71.6 (d, JP-C = 9.1 Hz). 31P NMR (CDCl3, δ/ppm):
37.3(d, 1 P, P-H, JP-H = 457.8 Hz). MS (FAB): m/z = 316
(Mþ). Anal. Calcd: C, 60.78; H, 6.70. Found: C, 59.72; H, 6.86.
˚
idealized positions and held fixed with C-H distances of 0.96 A.