[Pd(Phpy)(o-Ph2PC6H4CONHiPr)][PF6] (6a) (0.075 g, 56%).
Found: C, 52.9; H, 4.2; N, 3.9%. C33H30F6N2OP2Pd requires C,
52.6; H, 4.0; N, 3.7%. νmax/cmϪ1: (NH) 3372s; (CO) 1601vs,
(PF6) 842vs (Nujol). δH (200 MHz; CDCl3): 1.06 (br, 6H, CH3),
3.27 (m, 1H, CH), 6.26 (m, 1H), 6.53 (m, 1H), 6.75–7.02 (m,
3H), 7.18–7.55 (m, 14H), 7.64 (m, 1H), 7.79 (m, 1H), 8.25 (m,
1H), 8.78 (br, 1H, NH). δP (CDCl3): 35.6 (s). FAB-MS (positive
mode) m/z: 607 (M–PF6).
[Pd(Azb)(o-Ph2PC6H4COO)] (9) (0.032 g, 64%). Found: C,
62.5; H, 4.0; N, 4.5%. C31H23N2O2PPd requires C, 62.8; H, 3.9;
N, 4.7%. νmax/cmϪ1: (CO) 1720vs (Nujol). δH (200 MHz;
CDCl3): 6.24 (m, 1H), 6.68 (m, 1H), 6.81 (m, 1H), 7.13 (m, 1H),
7.31–7.58 (m, 15H), 7.98 (m, 1H), 8.18–8.23 (m, 2H), 8.36 (m,
1H). δP (CDCl3): 34.7 (s). FAB-MS (positive mode) m/z: 593
(Mϩ).
[Pd(Phpy)(o-Ph2PC6H4COO)] (10) (0.045 g, 82%). Found: C,
63.9; H, 4.1; N, 2.3%. C30H22NO2PPd requires C, 63.7; H, 3.9;
N, 2.5%. νmax/cmϪ1: (CO) 1642vs (Nujol). δH (200 MHz;
CDCl3): 6.35 (m, 1H), 6.56 (m, 1H), 6.92–7.00 (m, 2H), 7.41–
7.70 (m, 14H), 8.04–8.10 (m, 2H), 8.33 (m, 1H), 8.98 (m, 1H).
δP (CDCl3): 35.0 (s). FAB-MS (positive mode) m/z: 566 (Mϩ).
[Pd(Bzq)(o-Ph2PC6H4COO)] (11) (0.044 g, 86%). Found: C,
65.3; H, 3.6; N, 2.5%. C32H22NO2PPd: C, 65.1; H, 3.8; N, 2.4%.
νmax/cmϪ1: (CO) 1714vs (Nujol). δH (200 MHz; CDCl3): 6.40 (m,
1H), 6.90–7.00 (m, 2H), 7.33–7.69 (m, 16H), 8.31 (m, 1H), 8.49
(m, 1H), 9.28 (m, 1H). δP (CDCl3): 35.8 (s). FAB-MS (positive
mode) m/z: 590 (Mϩ).
[Pd(Bzq)(o-Ph2PC6H4CONHiPr)][PF6] (7a) (0.112 g, 77%).
Found: C, 54.0; H, 4.1; N, 3.6%. C35H30F6N2OP2Pd requires C,
54.1; H, 3.9; N, 3.6%. νmax/cmϪ1: (NH) 3357s; (CO) 1593vs,
(PF6) 843vs (Nujol). δH (200 MHz; CDCl3): 1.39 (br, 6H, CH3),
3.34 (m, 1H, CH), 6.37 (m, 1H), 6.91 (m, 3H), 7.32–7.70 (m,
16H), 8.28 (m, 2H), 9.00 (br, 1H, NH). δP (CDCl3): 35.7 (s).
FAB-MS (positive mode) m/z: 631 (M–PF6).
[Pd(Phox)(o-Ph2PC6H4CONHiPr)][PF6] (8a) (0.141 g, 91%).
Found: C, 50.0; H, 4.1; N, 3.6%. C31H30F6N2O2P2Pd requires C,
50.0; H, 4.0; N, 3.7%. νmax/cmϪ1: (NH) 3371s; (CO) 1597vs,
(PF6) 813vs (Nujol). δH (200 MHz; CDCl3): 1.00 (d, JHH = 6.4
Hz, 6H, CH3), 3.39 (m, 1H, CH), 4.04 (t, 2H, JHH = 9.2 Hz,
NCH2), 4.74 (t, 2H, J = 9.2 Hz, OCH2), 6.12 (dd, 1H, J = 7.5,
4.3 Hz), 6.61 (m, 1H), 6.75–6.93 (m, 2H), 7.27–7.52 (m, 13H),
8.20 (m, 1H). δP (CDCl3): 33.5 (s). FAB-MS (positive mode)
m/z: 599 (M–PF6).
[Pd(Azb)(o-Ph2PC6H4CONHPh)][PF6] (5b) (0.142 g, 94%).
Found: C, 54.5; H, 3.6; N, 5.3%. C37H29F6N3OP2Pd requires C,
54.6; H, 3.6; N, 5.1%. νmax/cmϪ1: (NH) 3370w; (CO) 1638s,
(PF6) 843vs (Nujol). δH (400 MHz; CDCl3): 6.11 (m, 1H), 6.49
(m, 1H), 6.77 (m, 1H), 6.85–6.99 (m, 10H), 7.18 (m, 1H), 7.21–
7.47 (m, 12H), 7.72 (m, 2H), 7.81 (m, 1H), 9.69 (br, 1H, NH).
δP (CDCl3): 39.9 (s). FAB-MS (positive mode) m/z: 665
(M–PF6).
[Pd(Phpy)(o-Ph2PC6H4CONHPr)][PF6] (6b) (0.122 g, 76%).
Found: C, 55.0; H, 3.7; N, 3.9%. C36H28F6N2OP2Pd requires C,
55.0; H, 3.6; N, 3.6%. νmax/cmϪ1: (NH) 3370s; (CO) 1671vs,
(PF6) 844vs (Nujol). δH (300 MHz; CDCl3): 6.29 (m, 1H), 6.46
(m, 1H), 6.89–7.00 (m, 3H), 7.07 (m, 2H), 7.24 (m, 1H),
7.31–7.57 (m, 13H), 7.54–7.88 (m, 6H), 10.10 (br, 1H, NH).
δP (CDCl3): 41.7 (s). FAB-MS (positive mode) m/z: 641
(M–PF6).
[Pd(Bzq)(o-Ph2PC6H4CONHPh)][PF6] (7b) (0.141 g, 93%).
Found: C, 56.1; H, 3.3; N, 3.3%. C38H28F6N2OP2Pd requires C,
56.3; H, 3.5; N, 3.4%. νmax/cmϪ1: (NH) 3360s; (CO) 1673vs,
(PF6) 841vs (Nujol). δH (400 MHz; CDCl3): 6.55 (m, 1H), 6.8–
6.99 (m, 5H), 7.30–7.99 (m, 19H), 8.40 (m, 1H), 9.83 (m, 1H).
10.66 (br, 1H, NH). δP (CDCl3): 46.2 (s). FAB-MS (positive
mode) m/z: 665 (M–PF6).
[Pd(Phox)(o-Ph2PC6H4COO)] (12) (0.045 g, 79%). Found: C,
60.1; H, 4.2; N, 2.7. C28H22NO3PPd: C, 60.3; H, 4.0; N, 2.5%.
νmax/cmϪ1: (CO) 1712vs (Nujol). δH (200 MHz; CDCl3): 4.14
(t, 2H, JHH = 9.4 Hz, NCH2), 4.72 (t, 2H, J = 9.4 Hz, OCH2),
6.19 (dd, 1H, J = 7.6, 4.4 Hz), 6.65 (m, 1H), 6.77–6.95 (m, 2H),
7.23–7.55 (m, 13H), 8.36 (m, 1H). δP (CDCl3): 33.5 (s).
FAB-MS (positive mode) m/z: 558 (Mϩ).
Complexes
[Pd(C^N)(o-Ph2PC6H4CO-NHR)(CH3COO)]
i
[R ؍
Pr, C^N ؍
phenylazophenyl (13a), 2-phenylpyridine
(14a),7,8-benzoquinolyl (15a), and 2-(2-oxazolinyl)phenyl (16a);
R ؍
Ph, C^N ؍
phenylazophenyl (13b), 2-phenylpyridine (14b),
7,8-benzoquinolyl (15b), and 2-(2-oxazolinyl)phenyl (16b)]. The
new complexes were obtained by treating [Pd(C^N)(µ-OAc)]2
with previously prepared 2-diphenylphosphine-N-isopropyl-
benzamide (a compounds) or 2-diphenylphosphine-N-phenyl-
benzamide (b compounds) in molar ratio 2 : 1, using dichloro-
methane as solvent and according to the following general
method. To a dichloromethane solution (10 mL) of the
corresponding precursor [Pd(C^N)(µ-OAc)]2 (60 mg) was
added solid 2-diphenylphosphinebenzamide. The resulting
solution was stirred for 30 min, and then concentrated to half
volume under reduced pressure. Addition of hexane caused
precipitation of the new complexes, which were filtered off, air
dried and recrystallised from dicholoromethane–hexane.
[Pd(Azb)(o-Ph2PC6H4CONHiPr)(CH3COO)] (13a) (0.077 g,
64%). Found: C, 62.2; H, 4.9; N, 6.3%; C36H34N3O3PPd requires
C, 62.3; H, 4.9; N, 6.1%. νmax/cmϪ1: (NH) 3223w; (CO) 1680s,
(CH3COO) 1600s (Nujol). δH (200 MHz; CDCl3): 1.06 (br, 6H,
CH3), 2.15 (br, 3H, CH3COO) 3.36 (m, 1H, CH), 6.34 (m, 1H),
6.63 (m, 1H), 7.02–7.14 (m, 2H), 7.26 (m, 1H), 7.43–7.52 (m,
14H), 7.81–7.84 (m, 2H), 7.98 (dd, 2H, J = 7.6, 1.4 Hz), 8.92
(br, 1H, NH). δC (CDCl3): 176.5 (s, COO), 41.8 (s, CH), 23.0
(s, CH3COO), 22.3 (s, CH3). δP (CDCl3): 43.3 (s). FAB-MS
(positive mode) m/z: 634 (M–CH3COO).
[Pd(Phox)(o-Ph2PC6H4CONHPh)][PF6] (8b) (0.149 g, 92%).
Found: C, 52.5; H, 3.6; N, 3.6%. C34H28F6N2O2P2Pd requires C,
52.4; H, 3.6; N, 3.6%. νmax/cmϪ1: (NH) 3376s; (CO) 1598vs,
(PF6) 813vs (Nujol). δH (200 MHz; CDCl3): 4.09 (m, 2H,
NCH2), 4.83 (t, 2H, JHH = 9.3 Hz, OCH2), 6.29 (dd, 1H, J = 7.5,
4.4 Hz), 6.75 (m, 1H), 6.92–7.34 (m, 4H), 7.49–7.81 (m, 16H),
8.21 (br, 1H), 9.51 (br, 1H, NH). δP (CDCl3): 36.8 (s). FAB-MS
(positive mode) m/z: 633 (M–PF6).
[Pd(Phpy)(o-Ph2PC6H4CONHiPr)(CH3COO)] (14a) (0.087 g,
69%). Found: C, 62.9; H, 4.8; N, 4.2%. C35H33N2O3PPd requires
C, 63.0; H, 5.0; N, 4.2%. νmax/cmϪ1: (NH) 3408w; (CO) 1594s,
(CH3COO) 1578s (Nujol). δH (200 MHz; CDCl3): 1.02 (d, 6H,
JHH = 5.0 Hz, CH3), 1.87 (br, 3H, CH3COO), 3.42 (m, 1H, CH),
6.39 (m, 2H), 6.88 (m, 2H), 7.20 (m, 1H), 7.32–7.45 (m, 14H),
7.72–8.04 (m, 2H), 8.48 (m, 1H), 9.10 (br, 1H, NH). δC (CDCl3):
176.9 (s, COO), 42.0 (s, CH), 23.3 (s, CH3COO), 22.4 (s, CH3).
δP (CDCl3): 42.9 (s). FAB-MS (positive mode) m/z: 607
(M–CH3COO).
Complexes [Pd(C^N)(o-Ph2PC6H4COO)] [C^N ؍
phenyl-
azophenyl (9), 2-phenylpyridine (10), 7,8-benzoquinolyl (11) and
2-(2-oxazolinyl)phenyl (12)]
The complexes were obtained by treating [Pd(C^N)(µ-OAc)]2
with 2-diphenylphosphinebenzoic acid (molar ratio 2 : 1) in
dichloromethane according to the following general method.
To a CH2Cl2 solution (10 mL) of the precursor [Pd(C^N)-
(µ-OAc)]2 (0.2 mmol) was added solid 2-diphenylphosphine-
benzoic acid (0.123 g, 0.4 mmol). The solution was then stirred
for 30 min, and after that concentrated under reduced pressure
to half volume. Addition of hexane caused precipitation of the
new complexes, which were filtered off, air dried and recrystal-
lized from dicholoromethane–diethyl ether.
[Pd(Bzq)(o-Ph2PC6H4CONHiPr)(CH3COO)] (15a) (0.079 g,
65%). Found: C, 64.3; H, 4.9; N, 4.3%. C37H33N2O3PPd requires
C, 64.3; H, 4.8; N, 4.1%. νmax/cmϪ1: (NH) 3400w; (CO) 1612s,
(CH3COO) 1556s (Nujol). δH (200 MHz; CDCl3): 1.05 (d, 6H,
JHH = 7.0 Hz, CH3), 1.82 (br, 3H, CH3COO) 3.40 (m, 1H, CH),
6.54 (m, 1H), 6.83 (m, 1H), 7.09–7.26 (m, 2H), 7.31–7.69 (m,
D a l t o n T r a n s . , 2 0 0 3 , 4 7 0 9 – 4 7 1 7
4714