3004 Organometallics, Vol. 20, No. 14, 2001
Ferna´ndez-Rivas et al.
8 (136 mg, 91%) as a colorless oil. 1H NMR (200 MHz, CDCl3):
δ 7.81 (d, J ) 8.1 Hz, 1H), 7.55 (dd, J ) 7.7, 1.6 Hz, 1H), 7.41
(t, J ) 7.7 Hz, 1H), 6.99 (td, J ) 8.1, 1.8 Hz, 1H), 4.66 (s, 2H),
1.00 (s, 9H), 0.17 (s, 6H). 13C{1H} NMR (75 MHz, CDCl3): δ
142.87, 138.60, 128.48, 128.11, 127.36, 95.76, 69.35, 25.96,
18.37, -3.01. Anal. Calcd for C13H21IOSi: C, 44.83; H, 6.08.
Found: C, 44.77; H, 5.78.
Exp er im en ta l Section
Gen er a l Con sid er a tion s. NMR spectra were recorded at
23 °C. Solvents were purified and dried using standard
procedures. Chromatographic purifications were carried out
using flash grade silica gel with distilled solvents. Trituration
involved stirring with the stated solvent, filtering, and washing
with the same solvent. All reactions were carried out under
an Ar atmosphere.
(Oxom eth ylen e-1,2-p h en ylen e)(tr ip h en ylp h osp h in e)-
p a lla d iu m Dim er (7). A mixture of 9 (1.27 g, 1.30 mmol) and
n-Bu4NF (1.19 g, 4.53 mmol) in THF (10 mL) was stirred at
23 °C for 24 h. Precipitated 7 was filtered and washed with
Et2O. The filtrate was evaporated and triturated with THF to
give additional 7 (combined yield: 610 mg, 99%), as a pale
yellow solid. Crystals of 7 were obtained from a solution of
CH2Cl2 at -20 °C. 1H NMR (200 MHz, CDCl3): δ 7.85 (m, 6H),
7.40 (m, 9H), 6.59 (t, J ) 7.5 Hz, 1H), 6.19 (m, 2H), 6.06 (t,
J ) 7.5 Hz, 1H), 3.66 (d, J ) 2.1 Hz, 2H). 13C{1H} NMR (75
MHz, CDCl3, DEPT): δ 160.14 (s, C), 137.57 [d, 2J (13C-31P) )
10.1 Hz, CH], 135.45 [d, 3J (13C-31P) ) 12.7 Hz, PPh3, CH],
131.38 [d, 1J (13C-31P) ) 47.8 Hz, PPh3, C], 130.48 (br s, PPh3,
A correct elemental analysis was not obtained for palladium
complexes 6, 7, 9, 11, 16, 17, and 22 due to the presence of
traces of ligands as impurities that could not be removed by
recrystallization. Complex 19 decomposed at room tempera-
ture.
Pd(PPh3)4 and Pd(dba)(bpy)37 were prepared according to
the described procedures.
36
tr a n s-[2-(H yd r oxym et h yl)p h en yl]iod ob is(t r ip h en yl-
p h osp h in e)p a lla d iu m (5). To a solution of o-iodobenzyl
alcohol (4; 250 mg, 1.06 mmol) in toluene (5 mL) was added
Pd(PPh3)4 (1.12 g, 0.96 mmol), and the resulting solution was
briefly sonicated and then heated at 40 °C for 3 h. The solid
was filtered and washed with Et2O to give 5 (680 mg, 82%) as
a white solid. This complex was recrystallized from THF-
3
CH), 128.30 [d, J (13C-31P) ) 10.7 Hz, PPh3, CH], 123.13 (br
s, CH), 122.53 (s, CH), 118.94 (s, CH), 75.79 (s, CH2) (the signal
of a quaternary carbon was not observed). 31P{1H} NMR (121.5
MHz, CDCl3): δ 44.42. MS (FAB+): m/z 1423 (M+ + 1, trimer,
0.02), 949 (M+ + 1, dimer, 1), 739, 737 (5), 736 (3), 475 (61)
(M+ + 1, monomer, 4), 474 (46), 473 (24). Anal. Calcd for
C50H42O2P2Pd2‚0.25CH2Cl2: C, 62.17; H, 4.41. Found: C, 62.28;
H, 4.55.
1
Et2O. H NMR (200 MHz, C6D6): δ 7.30 (m, 12H), 6.83 (br d,
J ) 7.5 Hz, 1H), 6.55 (m, 18H), 6.35 (d, J ) 7.0 Hz, 1H), 6.22
(t, J ) 7.0 Hz, 1H), 5.19 (t, J ) 7.5 Hz, 1H), 4.19 (d, J ) 7.0
Hz, 2H), -0.08 (t, J ) 7.0 Hz, 1H). 13C{1H} NMR (75 MHz,
CDCl3, DEPT): δ 158.35 [t, J (13C-31P) ) 2.5 Hz, C], 144.15
[t, J (13C-31P) ) 3.4 Hz, C], 134.81 [t, 2J (13C-31P) ) 6.1 Hz,
PPh3, CH], 134.02 [t, J (13C-31P) ) 4.4 Hz, CH], 131.74
[t, 1J (13C-31P) ) 23.2 Hz, PPh3, C], 129.98 (s, PPh3, CH),
128.35 (s, CH), 127.84 [t, 3J (13C-31P) ) 5.1 Hz, PPh3, CH],
125.70 (s, CH), 123.51 (s, CH), 68.14 [t, J (13C-31P) ) 3.4 Hz,
CH2]. 31P{1H} NMR (121.5 MHz, CDCl3): δ 23.03. Anal. Calcd
for C43H37IOPdP2: C, 59.70; H, 4.31. Found: C, 59.90; H, 4.65.
tr a n s-[2-(((ter t-Bu tyld im eth ylsilyl)oxy)m eth yl)p h en yl]-
iod obis(tr ip h en ylp h osp h in e)p a lla d iu m (9). To a suspen-
sion of Pd(PPh3)4 (1.32 g, 1.15 mmol) in toluene (10 mL) was
added 8 (370 mg, 1.06 mmol), and the mixture was heated at
40 °C for 6 h. The solid was filtered and washed with Et2O to
give 9 (955 mg, 92%) as a pale yellow solid. 1H NMR (200 MHz,
CDCl3): δ 7.50 (m, 12H), 7.40 (m, 18H), 6.85 (d, J ) 7.3 Hz,
1H), 6.51 (m, 2H), 6.27 (m, 1H), 4.48 (s, 2H), 0.86 (s, 9H), -0.05
(s, 6H). 13C{1H} NMR (75 MHz, CDCl3, DEPT): δ 156.73 (s,
Author: Please give the missing resonance value in the list
of 13C values.
[2-(Hydr oxym eth yl)ph en yl]iodo[1,1′-bis(diph en ylph os-
p h in o)fer r ocen e]p a lla d iu m (6). To a solution of 5 (100 mg,
0.12 mmol) in CH2Cl2 (3 mL) was added 1,1′-bis(diphenylphos-
phino)ferrocene (70 mg, 0.13 mmol) at 23 °C for 1 h. The
solvent was evaporated, and the residue was triturated with
2
C), 143.73 (s, C), 134.80 [d, J (13C-31P) ) 5.8 Hz, PPh3, CH],
134.14 [d, 3J (13C-31P) ) 3.9 Hz, CH], 131.91 [d, 1J (13C-31P) )
3
23.1 Hz, PPh3, C], 129.76 (br s, PPh3, CH), 127.72 [d, J (13C-
31P) ) 4.2 Hz, PPh3, CH], 126.40 (br s, CH), 125.30 (s, CH),
122.80 (s, C), 66.79 (s, CH2), 25.93 (s, 3 CH3), 18.29 (s, C), -2.78
(s, 2 CH3). 31P{1H} NMR (121.5 MHz, CDCl3): δ 23.16. FAB-
MS: m/z 851 (M+ + 1, 1), 589 (60), 483 (100), 263 (47).
1
Et2O to give 6 (100 mg, 98%) as a yellow solid. H NMR (200
MHz, CDCl3): δ 8.14-7.90 (m, 5H), 7.55 (m, 6H), 7.30 (m, 5H),
7.10 (t, J ) 7.0 Hz, 1H), 6.85 (m, 2H), 6.74-6.55 (m, 5H), 5.09
(s, 1H), 4.72 (dd, J ) 11.4, 3.0 Hz, 1H), 4.65 (s, 1H), 4.35 (s,
1H), 4.31 (s, 1H), 4.13 (s, 2H), 4.03 (dd, J ) 10.5, 10.3 Hz,
1H), 3.69 (s, 1H), 3.59 (s, 1H), 2.83 (dd, J ) 9.6, 3.4 Hz, 1H)
(the signal at δ 2.83 exchanged with D2O). 13C{1H} NMR (75
MHz, CDCl3; DEPT): δ 151.97 [d, J (13C-31P) ) 122.0 Hz, C],
144.35 [t, J (13C-31P) ) 3.6 Hz, C], 135.45 (m, PPh2, CH),
134.68 [d, J (13C-31P) ) 4.7 Hz, CH], 131.71 (m, PPh2, CH),
130.28 (m, PPh2, CH), 129.26 [td, J (13C-31P) ) 8.8 Hz, CH],
128.38 (m, PPh2, CH), 127.02 (m, PPh2, CH), 126.09 [d, J (13C-
31P) ) 7.8 Hz, CH], 123.46 (s, PPh2, CH), 76.35 (m, C), 74.21
(m, CH), 73.29 (m, CH), 72.39 (m, CH), 70.71 (m, CH), 69.58
[t, J (13C-P) ) 2.0 Hz, CH2]. 31P{1H} NMR (121.5 MHz,
CDCl3): δ 27.94 (d, J ) 33.2 Hz, 1P), 8.85 (d, J ) 33.5 H, 1P).
1-[((ter t-Bu t yld im et h ylsilyl)oxy)m et h yl]-2-iod ob en -
zen e (8). A mixture of 4 (100 mg, 0.42 mmol), chloro-tert-
butyldimethylsilane (77 mg, 0.51 mmol), DMAP (5 mg, 0.42
mmol), and Et3N (86 mg, 0.85 mmol) in DMF (10 mL) was
heated at 70 °C for 17 h. After being cooled to room temper-
ature, the mixture was partitioned between H2O and Et2O.
After the usual extractive workup, the solvent was evaporated.
The residue was purified by chromatography (hexane) to give
tr a n s-[2-(((ter t-Bu tyld im eth ylsilyl)oxy)m eth yl)p h en yl]-
iod obis(tr ip h en yla r sin e)p a lla d iu m (10). A mixture of Pd2-
(dba)3‚dba (330 mg, 0.57 mmol) and AsPh3 (790 mg, 2.58 mmol)
in acetone (5 mL) was stirred at 23 °C for 3 h to give a
precipitate. To the suspension was added 8 (300 mg, 0.86
mmol) and toluene (10 mL), and the mixture was heated at
40 °C for 17 h. The mixture was filtered through Celite, and
the filtrate was evaporated. The residue was triturated with
Et2O to give 10 (465 mg, 76%) as a pale yellow solid that was
1
recrystallized from CH2Cl2/Et2O. H NMR (200 MHz, CDCl3):
δ 7.35 (m, 30H), 6.88 (d, J ) 7.5 Hz, 1H), 6.56 (m, 2H), 6.34
(m, 1H), 4.49 (s, 2H), 0.81 (s, 9H), -0.15 (s, 6H). 13C{1H} NMR
(75 MHz, CDCl3; DEPT): δ 147.69 (C), 145.24 (C), 135.06 (CH),
133.93 (CH, AsPh3), 133.65 (C, AsPh3), 129.48 (CH, AsPh3),
128.31 (CH, AsPh3), 126.69 (CH), 125.35 (CH), 123.27 (CH),
66.56 (CH2), 25.87 (3 CH3), 19.86 (C), -2.64 (2 CH3). Anal.
Calcd for C49H51As2IOPdSi‚H2O: C, 54.23; H, 4.93. Found: C,
54.07; H, 4.81.
(Oxom et h ylen e-1,2-p h en ylen e)(t r ip h en yla r sin e)p a l-
la d iu m Dim er (11). A mixture of 10 (200 mg, 0.18 mmol) and
n-Bu4NF (97 mg, 0.87 mmol) in THF (2 mL) was stirred for
17 h at 23 °C. The solvent was evaporated, and the residue
was triturated with 1:3 CH2Cl2-Et2O to give 11 (83 mg, 86%)
(36) Cotton, F. A. Inorg. Synth. 1972, 13, 121.
(37) Takahashi, Y.; Ito, T.; Sakai, S.; Ishii, Y. J . Chem. Soc., Chem.
Commun. 1970, 1065.
1
as a pale yellow solid. H NMR (200 MHz, CDCl3): δ 7.83 (m,