72
G. Facchin et al. / Journal of Organometallic Chemistry 662 (2002) 70ꢃ76
/
1
k(NÅ
(C6H4, m); 4.81 (CH2, s); 0.20 (SiÃ
NMR (d, CDCl3): 167.5 (NÅC, s); 138.0ꢃ
m); 61.4 (CH2, s); 0.11 (SiÃCH3, s).
/
C) 1715 N mꢀ1. H-NMR (d, CDCl3): 7.60ꢃ
CH3, s). 13C{1H}-
124.4 (C6H4,
/
7.26
NMR (d, CDCl3): 132.4ꢃ
/
127.2 (C6H4, m); 61.4 (CH2,
Na]ꢂ.
/
s); 0.19 (SiÃCH3, s). ESI-MS: m/z 611 [Mꢂ
/
/
/
/
/
2.3.3. Synthesis of
ꢀ
ꢁ
2.2.3. Synthesis of 2-(hydroxymethyl)phenyl isocyanide
(3)
cis-[PtCl2{
/
CN(H)C6H4Ã
/
2-CH2O//}2] (6)
To a suspension of 4 (0.30 g, 4.44 mmol) in MeOH (20
ml) at r.t. was added TBAF (8 mg, 0.03 mmol). The
reaction mixture was stirred for 2 h to afford a white
To a solution of 2 (1.09 g, 5.31 mmol) in MeOH (15
ml) at r.t. under dinitrogen atmosphere was added
TBAF (four drops) and the reaction mixture was stirred
for 24 h. After that time, the solvent was evaporated
under reduced pressure to afford a pale green oil. Yield:
solid, which was filterd off, washed with Et2O (3ꢄ
/
5 ml)
and n-C6H14 (3ꢄ5 ml) and then dried under vacuum.
/
Yield: 0.18 g, 75%. Anal. Calc. for C16H14Cl2N2O2Pt: C,
36.10; H, 2.65; N, 5.26. Found: C, 36.07; H, 2.45; N,
0.60 mg, 84.7%. IR (
NÅC); k(NÅ
C) 1717 N mꢀ1
7.54ꢃ7.23 (C6H4, m); 4.73 (CH2, s); 3.47 (OH, s-br).
C, s); 138.0ꢃ
/
n˜; CH2Cl2): 3602 (m, OH), 2122 (s,
/
/
.
1H-NMR (d, CDCl3):
ꢀ ꢀ ꢀ
4.97%. IR (/n˜; KBr): 3452 (br, NH), 1543 (s, n˜asym
/
N*
/
C*
/
O) 332, 300 (m, PtCl, PE film). 1H-NMR (d,
/
ꢀ ꢀ ꢀ
13C{1H}-NMR (d, CDCl3): 166.8 (NÅ
/
/
Me2SO-d6): 12.42 (NH, s), 7.42ꢃ7.17 (C6H4, m); 5.41
/
(CH2, s). 13C{1H}-NMR (d, Me2SO-d6): 181.3 (Ccarbene
,
124.7 (C6H4, m); 61.3 (CH2, s).
1
s, JPtC 1590 Hz); 131.1ꢃ
/
115.5 (C6H4, m); 67.68 (CH2,
H]ꢂ.
s). ESI-MS: m/z 531 [Mꢀ
/
2.3. Synthesis of the complexes
2.3.1. Synthesis of cis-[PtCl2(CNC6H4Ã
/
2-
2.3.4. Synthesis of
CH2OSiMe3)2] (4)
To a solution of [(COD)PtCl2] (0.51 g, 1.37 mmol) in
CH2Cl2 (20 ml) at r.t. was added 2 (0.59 g, 2.87 mmol).
ꢀ
ꢁ
cis-[PdCl2{
/
CN(H)C6H4Ã
/
2-CH2O//}2] (7)
To a yellow solution of 5 (0.59 g, 1.00 mmol) in
MeOH (20 ml) at r.t. was added NaF (6 mg, 0.14 mmol).
The reaction mixture was stirred for 24 h to afford a
The yellowꢃ
this time, an IR spectrum showed the disappearance of
the CÅN absorption of the free isocyanide, while two
bands in the 2200ꢃ
2230 cmꢀ1 region were present. The
/orange solution was stirred for 1 h. After
creamꢃ/yellow precipitate, which was filterd off, washed
/
with Et2O (3ꢄ
/
10 ml) and n-C6H14 (3ꢄ10 ml) and then
/
/
dried under vacuum. Yield: 0.32 g, 72%. Anal. Calc. for
C16H14Cl2N2O2Pd: C, 43.32; H, 3.18; N, 6.31. Found:
C, 43.66; H, 3.06; N, 6.14%. IR (/n˜; KBr): 3477 (m, NH),
solvent was removed under reduced pressure to half of
the volume and then n-C6H14 (10 ml) and Et2O (20 ml)
were added to give a pale yellow precipitate, which was
ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ
N*C*
1548 (s, n˜asym/
/
/
O), 312, 283 (m, PdCl, PE film).
filtered off, washed with n-C6H14 (3ꢄ5 ml) and dried
under vacuum. Yield: 0.53 g, 58%. Anal. Calc. for
C22H30Cl2N2O2PtSi2: C, 39.05; H, 4.47; N, 4.14. Found:
/
1H-NMR (d, Me2SO-d6): 12.94 (NH, s), 7.43ꢃ
/
7.14
(C6H4, m), 5.45 (CH2, s). 13C{1H}-NMR (d, Me2SO-
d6): 200.9 (Ccarbene, s), d 129.5ꢃ115.5 (C6H4, m), 67.9
/
C, 39.48; H, 4.32; N, 4.14%. IR (
(s, NÅC) (2233, 2203 (s), KBr); k(NÅ
mꢀ1 (from CH2Cl2 data); 346, 324 (m, PtCl, PE film).
1H-NMR (d, CDCl3): 7.63ꢃ
7.36 (C6H4, m); 4.90 (CH2,
s); 0.18 (SiÃCH3, s). ESI-MS: m/z 699 [Mꢂ
Na]ꢂ.
/
n˜; CH2Cl2): 2229, 2196
(CH2, s).
/
/
C) 1893, 1837 N
/
/
/
2.3.5. Synthesis of cis-
ꢀ
ꢁ
cis-[PdCl2{
/
CN(H)C6H4Ã
/
2-CH2O//}(PPh3)] (8)
2.3.2. Synthesis of cis-[PdCl2(CNC6H4Ã
/2-
This complex was prepared by reaction of [PdCl(m-
Cl)(PPh3)]2 (0.40 g, 0.45 mmol) with 2 (0.19 g, 0.93
mmol) in MeOH (15 ml) and CH2Cl2 (5 ml) in the
presence of TBAF (three drops). The reaction mixture
was stirred for 2 h. Then the yellow precipitate was
CH2OSiMe3)2] (5)
This complex was prepared as described previously
for 4 starting from [PdCl2(CH3CN)2] (0.80 g, 3.09
mmol) in CH2Cl2 (30 ml) and 2 (1.33 g, 6.47 mmol).
The yellowꢃ/orange solution was stirred for 20 min and
filtered off, washed with Et2O (3ꢄ10 ml) and dried
/
then treated with n-C6H14 (30 ml) to give a white
precipitate, which was filtered off, washed with n-C6H14
under vacuum. Yield: 0.32 g, 72%. Anal. Calc. for
C26H22Cl2NOPPd: C, 54.52; H, 3.84; N, 2.45. Found: C,
(3ꢄ
Anal. Calc. for C22H30Cl2N2O2PdSi2: C, 44.94; H, 5.14;
N, 4.76. Found: C, 45.23; H, 5.14; N, 4.76%. IR (n˜;
CH2Cl2): 2229, 2215 (s, NÅC) (2238, 2213 (s), KBr);
k(NÅ
C) 1893, 1869 N mꢀ1 (from CH2Cl2 data); 349,
319 (m, PtCl, PE film). 1H-NMR (d, CDCl3): 7.64ꢃ
7.38
(C6H4, m); 4.91 (CH2, s); 0.19 (SiÃ
CH3, s). 13C{1H}-
/
5 ml) and dried under vacuum. Yield: 1.68 g, 93%.
54.27; H, 3.79; N, 2.14%. IR (/n˜; KBr): 3416 (m, NH),
ꢀ ꢀ ꢀ ꢀ ꢀ ꢀ
asymN*C*
1536 (s, n˜
/
/
/
O), 314, 276 (m, PdCl, PE film).
/
1H-NMR (d, Me2SO-d6): 13.18 (NH, s), 7.75ꢃ
7.40
/
/
(C6H4, m), 4.94 (CH2, s). 13C{1H}-NMR (d, Me2SO-
2
/
d6): 200.8 (Ccarbene, s, JCP 5.3 Hz), 134.4ꢃ
/
115.1 (C6H4,
m), 68.9 (CH2, s). 31P{1H}-NMR (d, Me2SO-d6): 25.4
/
/
(PPh3, s).