2686 Organometallics, Vol. 18, No. 14, 1999
Vicente et al.
1
(NH) ) 3185. H NMR (CDCl3): δ ) 1.82 (m, 1H, CH2, COD),
h and then filtered through MgSO4. The solvent was removed
to ca. 2 mL, and diethyl ether (25 mL) was added to precipitate
complex 7 as a pale yellow solid, which was collected and air-
2.28 (m, 1H, CH2, COD), 2.68 (m, 6H, CH2, COD), 3.85 (dd,
1H, CH2, 2J HH ) 12 Hz, 3J HH ) 10 Hz), 4.01 (dd, 1H, CH2, 2J HH
3
) 15 Hz, J HH ) 1.0 Hz), 4.21 (m, 1H of CH2 and NH), 4.86
dried. Yield: 77 mg, 0.12 mmol, 60%. Mp: 174-176 °C. ΛM )
2
3
(dd, 1H, CH2, J HH ) 15 Hz, J HH ) 4.8 Hz), 5.79 (m, 2H, CH,
COD), 6.29 (m, 1H, CH, COD), 6.41 (m, 1H, CH, COD), 6.76
(d, 1H, C6H4), 7.05 (m, 2H, C6H4), 7.12-7.20 (m, 2H, C6H4),
7.42-7.50 (m, 3H, Ph), 7.59-7.63 (m, 2H, Ph). 13C{1H}NMR:
δ ) 27.5, 28.7, 29.3, 30.0 (s, CH2, COD), 58.5, 61.6 (s, CH2),
109.4, 111.2 (s, CH, COD), 120.9 (s, CH, C6H4), 124.3, 124.9
(s, CH, COD), 126.8, 127.4, 129.3 (s, CH, C6H4 or Ph), 129.5,
130.0 (s, CH, Ph), 131.1 (s, CH, C6H4 or Ph), 136.0 (s, C, Ph),
149.8, 150.1 (s, C, C6H4).
118 Ω-1 cm2 mol-1 (5 × 10-4 mol L-1). Anal. Calcd for
C
28H31F3N2O3PdS (639.0): C, 52.63; H, 4.89; N, 4.38; S, 5.02.
Found: C, 52.32; H, 5.04; N, 4.45; S, 4.80. IR (Nujol, cm-1):
ν(NH) ) 3221. 1H NMR (CDCl3, -60 °C): δ ) 1.09 (s, 3H, Me),
1.81 (s, 3H, Me), 2.16 (s, 3H, Me), 2.17 (s, 3H, Me), 2.81
(apparent triplet, 1H, NH), 3.53 (apparent doublet, 1H, CH2),
4.11 (apparent doublet, 1H, CH2), 4.27 (apparent doublet, 1H,
CH2), 4.72 (apparent doublet, 1H, CH2), 6.68 (d, 1H, o-py, 3J HH
) 5.1 Hz), 6.89 (apparent triplet, 1H, m-py), 7.12-7.54 (m,
10H, C6H4 and Ph and p-py), 7.71 (apparent triplet, 1H, m-py),
8.83 (d, 1H, o-py, J HH ) 5.1 Hz).
Syn th esis of [P d {C(R)dC(R)C(R)dC(R)C6H4(CH2NH-
CH2P h )-2}Br ] [R ) Me (6a )]. To a suspension of complex 2
(400 mg, 0.523 mmol) in CH2Cl2 (20 mL) was added MeCt
CMe (300 µL, 3.82 mmol). After 8 h, a dark yellow solution
was formed, which was filtered through a plug of MgSO4. The
solvent was removed to ca. 2 mL, and n-pentane (25 mL) was
added to precipitate complex 6a as a yellow solid, which was
collected and air-dried. Yield: 306 mg, 0.624 mmol, 60%. Mp:
154-156 °C. ΛM ) 0 Ω-1 cm2 mol-1 (7.80 × 10-4 mol L-1). Anal.
Calcd for C22H26BrNPd (490.7): C, 53.84; H, 5.34; N, 2.85.
Found: C, 53.69; H, 5.38; N, 2.75. IR (Nujol, cm-1): ν(NH) )
Syn th esis of [P d {C(R)dC(R)C(R)dC(R)C6H4(CH2NH-
CH2P h )-2}(p h en )]OTf [R ) Me (8)]. To a solution of complex
6a (115 mg, 0.234 mmol) in acetone (15 mL) was added Tl-
(OTf) (85 mg, 0.24 mmol), and the mixture was stirred for 20
min; 1,10-phenanthroline monohydrate (47 mg, 0.24 mmol)
was added, and the resulting yellow suspension was stirred
for 1 h and then filtered through MgSO4. The solvent was
removed to ca. 1 mL, and diethyl ether (25 mL) was added to
precipitate complex 8 as a bright yellow solid, which was
collected and air-dried. Yield: 130 mg, 0.176 mmol, 75%. Mp:
164-166 °C. ΛM ) 122 Ω-1 cm2 mol-1 (5.9 × 10-4 mol L-1).
Anal. Calcd for C35H34F3N3O3PdS (739.7): C, 56.78; H, 4.63;
N, 5.68; S, 4.33. Found: C, 56.61; H, 4.68; N, 5.78; S, 4.33. IR
(Nujol, cm-1): ν(NH) ) 3245. 1H NMR (CDCl3): δ ) 1.03 (s,
3H, CH3), 1.57 (s, 3H, CH3), 1.65 (s, 3H, CH3), 1.76 (s, 3H,
3202. 1H NMR (CDCl3): δ ) 1.81 (s, 3H, Me), 1.85 (s, 3H, Me),
2
2.10 (s, 3H, Me), 2.12 (s, 3H, Me), 2.87 (dd, 1H, CH2, J HH
)
13.8 Hz, 3J HH ) 12.3 Hz), 3.40 (m, 1H, NH), 3.47 (dd, 1H, CH2,
2J HH ) 13.0 Hz, J HH ) 2 Hz), 4.04 (dd, 1H, CH2, J HH ) 13.5
3
2
3
3
Hz, J HH ) 2 Hz), 4.18 (dd, 1H, CH2, J HH ) 3 Hz), 7.10-7.45
(m, 9H, C6H4 and Ph).
2
CH3), 2.83 (m, 1H, NH), 4.43 (dd, 1H, CH2, J HH ) 12.3 Hz,
Syn th esis of [P d {C(R)dC(R)C(R)dC(R)C6H4(CH2NH-
CH2P h )-2}Br ] [R ) Et (6b)]. To a suspension of complex 2
(200 mg, 0.261 mmol) in CH2Cl2 (20 mL) was added EtCtCEt
(180 µL, 1.57 mmol). After 6 h, a dark yellow solution was
formed, which was filtered through a plug of MgSO4. The
solvent was removed to ca. 2 mL, and n-hexane (25 mL) was
added to precipitate complex 6b as a yellow solid, which was
collected and air-dried. Yield: 165 mg, 0.302 mmol, 58%. Mp:
145 °C. ΛM ) 0 Ω-1 cm2 mol-1 (6.90 × 10-4 mol L-1). Anal.
Calcd for C26H34BrNPd (546.9): C, 57.10; H, 6.27; N, 2.56.
Found: C, 59.92; H, 6.34; N, 2.61. IR (Nujol, cm-1): ν(NH) )
3J HH ) 5.4 Hz), 4.48 and 4.67 (AB part of ABX system, 2H,
2
3
3
CH2, J AB ) 12 Hz, J AX ) 17 Hz, J BX ) 10 Hz), 4.74 (dd, 1H,
2
3
CH2, J HH ) 12.3 Hz, J HH ) 4 Hz), 7.05 (m, 2H, C6H4), 7.19
(m, 1H, C6H4), 7.27-7.41 (m, 6H, C6H4 and C6H5), 7.90 (dd,
3
3
1H, H3, phen, J HH ) 4.8 Hz, J HH ) 8.1 Hz), 8.11 (s, 2H, H5,
3
3
phen), 8.42 (dd, 1H, H3, phen, J HH ) 4.8 Hz, J HH ) 8.1 Hz),
4
3
8.55 (dd, 1H, H2, phen, J HH ) 1.2 Hz, J HH ) 5.4 Hz), 8.67
4
3
(dd, 1H, H4, phen, J HH ) 1.2 Hz, J HH ) 8.4 Hz), 8.71 (dd,
4
3
1H, H4, phen, J HH ) 1.2 Hz, J HH ) 8.4 Hz), 9.59 (dd, 1H,
4
3
H2, phen, J HH ) 1.2 Hz, J HH ) 4.8 Hz).
1
3
3245. H NMR (CDCl3): δ ) 1.01 (t, 3H, Me, J HH ) 7.5 Hz),
Syn t h esis of [P d {C(dO)C(R )dC(R )C(R )dC(R )C6H 4-
(CH2NHCH2P h )-2}Br ] [R ) Me (9a )]. CO was bubbled
through a solution of complex 6a (250 mg, 0.509 mmol) in CH2-
Cl2 (30 mL) for 1.5 h. After 8 h of stirring, the solution was
filtered through a plug of MgSO4. The solvent was removed
to ca. 2 mL, and diethyl ether (25 mL) was added to precipitate
complex 9a as a yellow solid, which was collected and air-dried.
Yield: 190 mg, 0.366 mmol, 72%. Mp: 187-188 °C. ΛM ) 0
3
3
1.07 (t, 3H, Me, J HH ) 7.5 Hz), 1.17 (t, 3H, Me, J HH ) 7.5
Hz), 1.34 (t, 3H, Me, 3J HH ) 7.5 Hz), 1.91 (m, 2H, Et), 2.14 (m,
1H, Et), 2.39 (m, 4H, Et), 2.60 (m, 1H, Et), 2.77 (apparent t,
2
3
1H, CH2, J HH ) J HH ) 13.0 Hz), 3.38 (m, 1H, NH), 3.38 (d,
2
2
1H, CH2, J HH ) 13.0 Hz), 4.07 (dd, 1H, CH2, J HH ) 13.5 Hz,
3J HH ) 1.5 Hz), 4.14 (dd, 1H, CH2, J HH ) 13.5 Hz, J HH ) 3.0
2
3
Hz), 7.07-7.46 (m, 9H, C6H4 and Ph).
Ω-1 cm2 mol-1 (6.20 × 10-4 mol L-1). Anal. Calcd for C23H26
-
Syn th esis of [P d {C(R)dC(R)C(R)dC(R)C6H4(CH2NH-
CH2P h )-2}Br ] [R ) P h (6c)]. To a suspension of complex 2
(100 mg, 0.131 mmol) in CH2Cl2 (25 mL) was added PhCt
CPh (187 mg, 1.04 mmol). After 12 h, a yellow solution was
formed, which was filtered through a plug of MgSO4. The
solvent was removed to ca. 2 mL, and diethyl ether (25 mL)
was added to precipitate complex 6c as a bright yellow solid,
which was collected and air-dried. Yield: 130 mg, 0.176 mmol,
67%. Mp: 175-176 °C. ΛM ) 0 Ω-1 cm2 mol-1 (5.68 × 10-4 mol
L-1). Anal. Calcd for C42H34BrNPd (739.0): C, 68.25; H, 4.64;
N, 1.89. Found: C, 67.97; H, 4.53; N, 2.02. IR (Nujol, cm-1):
BrNOPd (518.8): C, 53.25; H, 5.05; N, 2.70. Found: C, 53.14;
H, 4.95; N, 2.68. IR (Nujol, cm-1): ν(NH) ) 3225, ν(CO) ) 1675.
1H NMR (CDCl3): δ ) 1.68 (s, 3H, Me), 1.76 (s, 3H, Me), 2.11
2
(s, 3H, Me), 2.15 (s, 3H, Me), 2.73 (apparent t, 1H, CH2, J
HH
) 3J HH ) 13.0 Hz), 3.52 (d, 1H, CH2, 2J HH ) 13.0 Hz), 3.66 (m,
1H, NH), 4.03 (d, 1H, CH2, 2J HH ) 13.0 Hz), 4.31 (dd, 1H, CH2,
3
2J HH ) 13.0 Hz, J HH ) 3 Hz), 7.07-7.46 (m, 9H, C6H4 and
Ph).
Syn t h esis of [P d {C(dO)C(R )dC(R )C(R )dC(R )C6H 4-
(CH2NHCH2P h )-2}Br ] [R ) Et (9b)]. CO was bubbled
through a solution of complex 6b (160 mg, 0.293 mmol) in CH2-
Cl2 (30 mL) for 1.5 h. After 8 h of stirring, the solution was
filtered through a plug of MgSO4. The solvent was removed
to ca. 2 mL, and diethyl ether (25 mL) was added to precipitate
complex 9b as a yellow solid, which was collected and air-dried.
Yield: 160 mg, 0.278 mmol, 95%. Mp: 178-180 °C. ΛM ) 0
1
2
ν(NH) ) 3215. H NMR (CDCl3): δ ) 2.70 (dd, 1H, CH2, J HH
3
2
) 13.5 Hz, J HH ) 3 Hz), 3.22 (dd, 1H, CH2, J HH ) 13.5 Hz,
3J HH ) 2 Hz), 3.35 (t, 1H, CH2, J HH ) J HH ) 12.9 Hz), 3.55
2
3
2
(m, 1H, NH), 4.45 (d, 1H, CH2, J HH ) 12.9 Hz), 6.70-7.70
(m, 29H, C6H4 and Ph).
Syn th esis of [P d {C(R)dC(R)C(R)dC(R)C6H4(CH2NH-
CH2P h )-2}(p y)]OTf [R ) Me (7)]. To a solution of complex
6a (100 mg, 0.204 mmol) in acetone (15 mL) was added Tl-
(OTf) (OTf ) CF3SO3) (73 mg, 0.20 mmol), and the mixture
was stirred for 20 min. Pyridine (0.1 mL, 1.00 mmol) was
added, and the resulting yellow suspension was stirred for 6
Ω-1 cm2 mol-1 (5.56 × 10-4 mol L-1). Anal. Calcd for C27H34
-
BrNOPd (574.9): C, 56.41; H, 5.96; N, 2.44. Found: C, 56.46;
H, 6.09; N, 2.45. IR (Nujol, cm-1): ν(NH) ) 3215, ν(CO) ) 1680.
1H NMR (CDCl3): δ ) 1.06 (t, 3H, Me, 3J HH ) 7.5 Hz), 1.08 (t,
3
3
3H, Me, J HH ) 7.5 Hz), 1.26 (t, 3H, Me, J HH ) 7.5 Hz), 1.49