´
J. L. Serrano, I. J. S. Fairlamb, G. Sanchez et al.
FULL PAPER
1720 s (νCO), 1602 s (νCO). 1H NMR (200 MHz, CDCl3): δ ϭ [NBu4][Pd{C4(COOMe)4}(pht)(py)] (3d): Yield: 0.042 g (76%). M.p.
2.20 (s, 3 H, MeC6H4), 2.33 (m, 4 H, suc), 3.54 (s, 3 H, COOMe),
3.55 (s, 3 H, COOMe), 3.66 (s, 3 H, COOMe), 3.68 (s, 3 H, CO-
168 °C (dec.). C41H57N3O10Pd (858.34): calcd. C 57.4, H 6.7, N
4.9; found C 57.1, H 7.0, N 5.0. IR (nujol): ν˜ ϭ 1698 s (νCO), 1644
OMe), 5.18 (br., 2 H, NH2), 6.75 (d, J ϭ 8.2 Hz, 2 H, C6H4), 6.91 s (νCO). 1H NMR (200 MHz, CDCl3): δ ϭ 3.16 (s, 3 H, COOMe),
(d, J ϭ 8.2 Hz, 2 H, C6H4) ppm. 13C{1H} NMR (200 MHz, 3.25 (s, 3 H, COOMe), 3.55 (s, 3 H, COOMe), 3.59 (s, 3 H, CO-
CDCl3): δ ϭ 20.6 (MeC6H4), 31.8 (suc), 50.8 (COOMe), 51.1 OMe), 7.19 (m, 2 H, py), 7.37 (m, 2 H, pht), 7.50 (m, 2 H, pht),
(COOMe) ppm. FAB-MS (negative mode): m/z
ϭ
595 7.59 (m, 1 H, py), 8.74 (m, 2 H, py) ppm. 13C{1H} NMR
[Pd{C4(COOMe)4}(suc)(p-MeC6H4NH2)]Ϫ, 488 [Pd{C4{COOMe)4} (300 MHz, CDCl3): δ ϭ 50.1 (COOMe), 50.7 (COOMe), 50.8 (CO-
(suc)]Ϫ.
OMe), 50.9 (COOMe) ppm. FAB-MS (negative mode): m/z ϭ 928
[Pd2{C4(COOMe)4}2(suc)]Ϫ, 536 [Pd(C4{COOMe}4(pht)]Ϫ.
[NBu4][Pd{C4(COOMe)4}(suc)(tht)] (2f): Yield: 0.044 g (79%). M.p.
185 °C (dec.). C36H60N2O10PdS (819.36): calcd. C 52.8, H 7.4, N
3.4, S 3.9; found C 53.0, H 7.6, N 3.2, S 4.2. IR (nujol): ν˜ ϭ 1698
[NBu4][Pd{C4(COOMe)4}(pht)(p-MeC6H4NH2)] (3e): Yield: 0.037
g (65%). M.p. 93 °C (dec.). C43H61N3O10Pd (886.40): calcd. C 58.3;
H 6.9, N 4.7; found C 58.6, H 7.1, N 5.0. IR (nujol): ν˜ ϭ 1698 s
1
s (νCO), 1620 s (νCO). H NMR (300 MHz, CDCl3): δ ϭ 1.86 (m,
1
4 H, tht), 2.47 (m, 4 H, suc), 2.93 (m, 4 H, tht), 3.54 (s, 3 H,
COOMe), 3.56 (s, 3 H, COOMe), 3.60 (s, 3 H, COOMe), 3.67 (s,
3 H, COOMe) ppm. 13C{1H} NMR (300 MHz, CDCl3): δ ϭ 30.2
(tht), 32.4 (suc), 35.1 (tht), 50.6 (COOMe), 50.8 (COOMe),
50.9 (COOMe), 51.0 (COOMe) ppm. FAB-MS (negative mode):
(νCO), 1646 s (νCO). H NMR (200 MHz, CDCl3): δ ϭ 2.11 (s, 3
H, MeC6H4), 3.24 (s, 3 H, COOMe), 3.52 (s, 3 H, COOMe), 3.66
(s, 3 H, COOMe), 3.71 (s, 3 H, COOMe), 5.34 (br., 2 H, NH2),
6.75 (m, 4 H, C6H4), 7.44 (m, 2 H, pht), 7.56 (m, 2 H, pht) ppm.
13C{1H} NMR (200 MHz, CDCl3): δ ϭ 20.5 (MeC6H4), 50.7 (CO-
OMe), 50.8 (COOMe), 51.1 (COOMe), 51.2 (COOMe) ppm. FAB-
MS (negative mode): m/z ϭ 536 [Pd{C4(COOMe)4}(pht)]Ϫ.
m/z
ϭ
595 [Pd{C4(COOMe)4}(suc)(p-MeC6H4NH2)]Ϫ, 488
[Pd{C4(COOMe)4} (suc)]Ϫ.
Complexes [NBu4][Pd(C4{COOMe}4(pht)L] [L ؍
PPh3 (3a), P(p-
C6H4F)3 (3b), PBu3 (3c), py (3d), p-MeC6H4NH2 (3e), tetrahydro-
thiophene (3f)]: A stoichiometric amount of ligand (0.064 mmol)
was added to a solution of complex 3 (0.05 g, 0.032 mmol) in ace-
tone. The solution was stirred at room temperature for 30 min and
the solvent was then partly evaporated under reduced pressure to
approximately one-third of the initial volume. The addition of di-
ethyl ether caused the formation of yellow or pale-yellow solids,
which were filtered off, washed with diethyl ether and air-dried.
The compounds were recrystallized from dichloromethane/diethyl
ether.
[NBu4][Pd{C4(COOMe)4}(pht)(tht)] (3f): Yield: 0.036 g (65%). M.p.
180 °C (dec.). C40H60N2O10PdS (867.41): calcd. C 55.4, H 7.0, N
3.2, S 3.7; found C 55.6, H 7.3, N 3.4, S 4.0. IR (nujol): ν˜ ϭ 1698
1
s (νCO), 1644 s (νCO). H NMR (200 MHz, CDCl3): δ ϭ 1.82 (m,
4 H, tht), 2.98 (m, 4 H, tht), 3.10 (s, 3 H, COOMe), 3.58 (s, 3 H,
COOMe), 3.62 (s, 3 H, COOMe), 3.71 (s, 3 H, COOMe), 7.45 (m,
2 H, pht), 7.58 (m, 2 H, pht) ppm. 13C{1H} NMR (200 MHz,
CDCl3): δ ϭ 30.1 (tht), 35.0 (tht), 50.6 (COOMe), 50.7 (COOMe),
50.9 (COOMe) ppm. FAB-MS (negative mode): m/z ϭ 536
[Pd{C4(COOMe)4}(pht)]Ϫ.
Preparation of the Complexes [NBu4][Pd{C4(COOMe)4}(mal)L]
[L ؍
PPh3 (4a), P(p-C6H4F)3 (4b), PBu3 (4c), py (4d), p-
[NBu4][Pd{C4(COOMe)4}(pht)(PPh3)] (3a): Yield: 0.051 g (77%).
M.p. 95 °C. C54H67N2O10PPd (1041.5): calcd. C 62.3, H 6.5, N 2.7;
found C 62.0, H 6.8, N 3.1 IR (nujol): ν˜ ϭ 1694 s (νCO), 1640 s
MeC6H4NH2 (4e), tetrahydrothiophene (4f)]:
A stoichiometric
amount of ligand (0.068 mmol) was added to a solution of the di-
nuclear complex [NBu4]2[Pd(C4{COOMe}4(µ-mal)]2 (4; 0.05 g,
0.034 mmol) in acetone. The solution was stirred at room tempera-
ture for 30 min, and then the solvent was partly evaporated under
reduced pressure to approximately one-third of the initial volume.
The addition of diethyl ether caused the formation of yellow or
pale-yellow solids, which were filtered off, washed with diethyl
ether and air-dried. The compounds were recrystallised from di-
chloromethane/diethyl ether.
1
(νCO). H NMR (200 MHz, CDCl3): δ ϭ 2.51 (s, 3 H, COOMe),
3.25 (s, 3 H, COOMe), 3.51 (s, 3 H, COOMe), 3.55 (s, 3 H, CO-
OMe), 7.57 (m, 13 H, pht ϩ PPh3), 7.60 (m, 6 H, PPh3) ppm.
31P{1H} NMR (200 MHz, CDCl3): δ ϭ 28.3 (s) ppm. FAB-MS
(negative mode): m/z ϭ 798 [Pd{C4(COOMe)4}(pht)(PPh3)]Ϫ, 536
[Pd{C4(COOMe)4}(pht)]Ϫ.
[NBu4][Pd{C4(COOMe)4}(pht)(P{p-C6H4F}3)] (3b): Yield: 0.057 g
(81%). M.p. 165 °C (dec.). C54H64F3N2O10PPd (1095.5): calcd. C
59.2, H 5.9, N 2.6; found C 59.0, H 6.1, N 2.9. IR (nujol): ν˜ ϭ
1694 s (νCO), 1640 s (νCO). 1H NMR (200 MHz, CDCl3): δ ϭ
2.61 (s, 3 H, COOMe), 3.26 (s, 3 H, COOMe), 3.52 (s, 3 H, CO-
OMe), 3.55 (s, 3 H, COOMe), 6.86 [m, 6 H, P(p-C6H4F)3], 7.27 [m,
4 H, pht ϩ P(p-C6H4F)3], 7.57 [m, 6 H, pht ϩ P(p-C6H4F)3] ppm.
19F{1H} NMR (200 MHz, CDCl3): δ ϭ Ϫ111.2 (td, 3J ϭ 5.6, 5J ϭ
3.8 Hz, 3 F) ppm. 31P{1H} NMR (200 MHz, CDCl3): δ ϭ 26.5
(s) ppm. FAB-MS (negative mode): m/z ϭ 852 [Pd{C4(COOMe)4}
(pht){P(p-C6H4F)3}]Ϫ, 536 [Pd{C4(COOMe)4}(pht)]Ϫ.
[NBu4][Pd{C4(COOMe)4}(mal)(PPh3)] (4a): Yield: 0.043 g (64%).
M.p. 140 °C (dec.). C50H65N2O10PPd (991.47): calcd. C 60.6, H
6.6, N 2.8; found C 60.4, H 6.9, N 3.0. IR (nujol): ν˜ ϭ 1698 s
1
(νCO), 1636 s (νCO. H NMR (300 MHz, CDCl3): δ ϭ 2.50 (s, 3
H, COOMe), 3.43 (s, 3 H, COOMe), 3.49 (s, 3 H, COOMe), 3.55
(s, 3 H, COOMe), 5.91 (s, 2 H, mal), 7.27 (m, 9 H, PPh3), 7.60 (m,
6 H, PPh3) ppm. 31P{1H} NMR (300 MHz, CDCl3): δ ϭ 28.1 (s)
ppm.
FAB-MS
(negative
mode):
m/z
ϭ
748
[Pd{C4(COOMe)4}(mal)(PPh3)]Ϫ, 486 [Pd{C4(COOMe)4}(mal)]Ϫ.
[NBu4][Pd{C4(COOMe)4}(pht)(PBu3)] (3c): Yield: 0.038 g (60%).
M.p. 132 °C (dec.). C48H79N2O10PPd (981.56): calcd. C 58.7, H
8.1, N 2.8; found C 58.5, H 8.4, N 2.7. IR (nujol): ν˜ ϭ 1692 s
[NBu4][Pd{C4(COOMe)4}(mal)(P{p-C6H4F)3]] (4b): Yield: 0.047 g
(66%). M.p. 160 °C (dec.). C50H62F3N2O10PPd (1045.4): calcd. C
(νCO), 1646 s (νCO). 1H NMR (200 MHz, CDCl3): δ ϭ 0.75 (t, 57.4, H 6.0, N 2.7; found C 57.2, H 6.3, N 2.9. IR (nujol): ν˜ ϭ
J ϭ 7.2 Hz, 9 H, PBu3), 1.19 (m, 6 H, PBu3), 1.46 (m, 12 H, 1694 s (νCO), 1632 s (νCO). 1H NMR (200 MHz, CDCl3): δ ϭ
PBu3), 3.07 (s, 3 H, COOMe), 3.45 (s, 3 H, COOMe), 3.57 (s, 3 H,
2.60 (s, 3 H, COOMe), 3.43 (s, 3 H, COOMe), 3.51 (s, 3 H, CO-
COOMe), 3.60 (s, 3 H, COOMe), 7.40 (m, 2 H, pht), 7.54 (m, 2 OMe), 3.55 (s, 3 H, COOMe), 5.99 (s, 2 H, mal), 6.97 [m, 6 H, P(p-
H, pht) ppm. 31P{1H} NMR (200 MHz, CDCl3): δ ϭ 3.2 (s) ppm.
FAB-MS (negative mode): m/z 738 [Pd{C4(COOMe)4}
(pht)(PBu3)]Ϫ, 536 [Pd{C4(COOMe)4}(pht)]Ϫ.
C6H4F)3], 7.56 [m, 6 H, P(p-C6H4F)3] ppm. 19F{1H} NMR
(200 MHz, CDCl3): δ ϭ Ϫ111.1 (td, 3J ϭ 5.6, 5J ϭ 3.8 Hz, 3 F)
ppm. 31P{1H} NMR (200 MHz, CDCl3): δ ϭ 26.4 (s) ppm. FAB-
ϭ
2712
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2004, 2706Ϫ2715