J. J. Fernández, J. M. Vila et al.
FULL PAPER
[Pd{4-Me-2-CH2C6H3C(H)=N(2-OC6H4)}]n[Pd{2,4-(Me)2C6H2C-
(H)=N(2-OC6H4)}]4–n (n = 0–4): The mixture was prepared by fol-
lowing a procedure similar to that used for 1a, but with reaction
times of 5 h, 24 h and 3 d and reaction temperatures of 40, 60 and
80 °C. The components of the mixture could not be separated by
column chromatography or by other methods. Yield: 30 mg, 30%.
C60H52N4O4Pd4 (1318.75): calcd. C 54.4, H 4.3, N 4.2; found C
(200 MHz, CDCl3): δ = 2.28 (s, 3 H, Me), 2.93 (d, 3JCH ,P = 5.8 Hz,
2
2 H, -CH2-), 6.43 (t, 3JH10,H9 = 7.5 Hz, 1 H, 10-H), 6.66 (d, 3JH3,H4
3
= 7.8 Hz, 1 H, 3-H), 6.89 (m, 2 H, 4-H, 11-H), 7.09 (t, JH9,H8
=
4
3
7.5 Hz, JH11,H9 = 1.5 Hz, 1 H, 9-H), 7.25 (d, JH9,H8 = 7.5 Hz, 1
H, 8-H), 7.27 (s, 1 H, 6-H), 8.32 (d, 4JH ,P = 12.7 Hz, 1 H, Hi) ppm.
i
31P{1H} NMR (80.96 MHz, CDCl3): δ = 33.8 (s) ppm. FAB-MS:
m/z = 592 [M]+.
54.3, H 4.3, N 4.0. IR: ν = 1598 (s, νC=N) cm–1. 1H NMR
˜
Compounds 2d and 2dЈ were prepared by a similar procedure to
the one described for 2a using as starting material the mixture of
isomers 1d/1dЈ. The compounds were obtained as a mixture [in a
1:0.5 (2d/2dЈ) molar ratio] from which the pure compounds could
not be isolated by column chromatography or by other methods.
(200 MHz, CDCl3): δ = 3.62 (d, Jgem(H,H) = 13.5 Hz, 1 H, -CH2-),
3.53 (d, Jgem(H,H) = 14.0 Hz, 1 H, -CH2-), 3.83 (d, Jgem(H,H)
=
13.0 Hz, 1 H, -CH2-), 3.84 (d, Jgem(H,H) = 14.0 Hz, 1 H, -CH2-),
3.92 (d, Jgem(H,H) = 13.7 Hz, 1 H, -CH2-) ppm. 1H NMR
(200 MHz, [D6]dmso): δ = 2.14 (s, 3 H, Me), 2.34, 2.35 (s, 6 H,
MeЈ), 3.26 (s, 2 H, -CH2-), 8.41 (s, 1 H, Hi), 8.82 (s, 1 H, Hi) ppm.
[Pd{4-Me-2-CH2C6H3C(H)=N(2-OC6H4)}(PPh3)]
(2d)
and
[Pd{2,4-(Me)2C6H2C(H)=N(2-OC6H4)}(PPh3)] (2dЈ): Yield: 23 mg,
Compound 1e was prepared similarly as a yellow solid.
50%. C33H29NOPPd (592.98): calcd. C 66.8, H 4.9, N 2.4; found
[Pd{2-O-4,6-(MeO)2C6H2C(H)=N(2-OC6H4)}]4
(1e):
Yield:
C 66.3, H 4.7, N 2.3. IR: ν = 1581 (s, νC=N) cm–1. 1H NMR
˜
117 mg, 75%. C60H52N4O16Pd4 (1510.75): calcd. C 47.7, H 3.5, N
(200 MHz, CDCl3): δ = 2.67 (s, 6 H, MeЈ), 2.25 (s, 3 H, Me), 2.93
1
3.7; found C 47.5, H 3.4, N 3.5. IR: ν = 1612 (s, νC=N) cm–1. H
(d, 3JCH ,P = 5.8 Hz, 2 H, -CH2-), 5.67 (d, 4JH5,P = 3.4 Hz, 1 H, 5Ј-
˜
2
4
4
NMR (200 MHz, CDCl3): δ = 3.70, 3.82 (s, 6 H, MeO), 5.57, 5.73
H), 8.20 (d, JH ,P = 10.3 Hz, 1 H, HiЈ), 8.32 (d, J
= 12.7 Hz,
Hi,P
i
(d, H5, 4JH5,H3 = 1.9 Hz, 2 H, 3-H), 6.59 (t, 3JH9,H8 = 7.5 Hz, 1 H,
1 H, Hi) ppm. 31P{1H} NMR (80.96 MHz, CDCl3): δ = 34.6 (2dЈ),
3
9-H), 7.09 (m, 2 H, 8-H, 10-H), 7.71 (s, 1 H, Hi), 8.33 (d, JH11,H10 33.8 (s) (2d) ppm.
= 8.3 Hz, 1 H, 11-H) ppm.
[Pd{2-O-4,6-(MeO)2C6H2C(H)=N(2-OC6H4)}(PPh3)] (2e): Yield:
Compound 1f was prepared similarly as a red solid. Different reac-
tion times (5 h, 24 h and 5 d) were used with similar yields.
29 mg, 60%. C33H28NO4PPd (639.97): calcd. C 61.9, H 4.4, N 2.2;
found C 61.5, H 4.1, N 2.0. IR: ν = 1611 (s, νC=N) cm–1. 1H NMR
˜
(200 MHz, CDCl3): δ = 3.67, 3.88 (s, 6 H, MeO), 5.63, 5.78 (d,
[Pd{2-OC6H4C(H)=N(2-OC6H4)}]4 (1f): Yield: 118 mg, 86%.
3
4JH5,H3 = 2.2 Hz, 2 H, 3-H, 5-H), 6.64 (t, JH10,H9 = 7.5 Hz, 1 H,
C52H36N4O8Pd4 (1270.75): calcd. C 49.2, H 2.8, N 4.4; found C
3
10-H), 6.90 (d, JH11,H10 = 7.5 Hz, 1 H, 11-H), 7.03 (t, 1 H, 9-H),
48.9, H 2.8, N 4.3. IR: ν = 1609 (s, νC=N) cm–1. 1H NMR
˜
3
4
7.72 (d, JH9,H8 = 8.3 Hz, 1 H, 8-H), 9.12 (d,
J
= 18.1 Hz, 1
3
3
Hi,P
(200 MHz, [D6]dmso): δ = 7.17 (m, JH10,H11 = 8.3 Hz, JH10,H9
=
H, Hi) ppm. 31P{1H} NMR (80.96 MHz, CDCl3): δ = 23.4 (s) ppm.
FAB-MS: m/z = 639 [M]+.
4
3
7.0 Hz, JH10,H8 = 1.3 Hz, 1 H, 10-H), 7.30 (m, JH,H = 8.0 Hz,
3JH,H = 6.8 Hz, JH,H = 1.3 Hz, 1 H), 7.34 (dd, H8, JH9,H8
=
4
3
3
4
8.3 Hz, 1 H), 7.57 (dd, JH,H = 8.7 Hz, JH,H = 1.3 Hz, 1 H), 7.60
(m, JH,H = 1.3 Hz, 1 H, 9-H), 7.93 (m, JH,H = 8.6 Hz, JH,H
6.8 Hz, JH,H = 1.8 Hz, 1 H), 8.18 (dd, JH,H = 8.0 Hz, JH,H
[Pd{2-OC6H4C(H)=N(2-OC6H4)}(PPh3)] (2f): Yield: 25 mg, 66%.
4
3
3
=
=
C31H24NO2PPd (579.92): calcd. C 64.2, H 2.4, N 4.2; found C 64.3,
4
3
4
H 2.3, N 4.0. IR: ν = 1603 (s, νC=N) cm–1. 1H NMR (200 MHz,
˜
3
1.8 Hz, 1 H), 8.33 (dd, 1 H, 11-H), 8.94 (1 H, Hi) ppm. FAB-MS: CDCl3): δ = 6.61 (d, JH5,H4 = 8.5 Hz, 1 H, 5-H), 6.7 (m, 2 H, 3-
m/z = 637 [M/2]+.
H, 10-H), 6.92 (dd, 3JH11,H10 = 8.3 Hz, JH11,H9 = 1.2 Hz, 1 H, 11-
3
3
3
H), 7.08 (dt, JH10,H9 = 6.9 Hz, JH9,H8 = 8.3 Hz, 1 H, 9-H), 7.22
[Pd{2,3,4-(MeO)3C6HC(H)=N(2-O-5-tBuC6H3)}(PPh3)] (2a): PPh3
(6.99 mg, 0.026 mmol) was added to a suspension of 1a (12 mg,
0.006 mmol) in acetone (15 cm3). The mixture was stirred for 12 h,
and the solvent was removed to give a violet solid, which was
recrystallized from acetone/hexane. Yield: 15 mg, 80%.
C38H38NO4PPd (710.11): calcd. C 64.3, H 5.4, N 1.9; found C 64.3,
3
3
3
(dt, JH5,H4 = 8.6 Hz, JH4,H3 = 6.8 Hz, JH4,H2 = 1.8 Hz, 1 H, 4-
3
4
H), 7.74 (dd, JH9,H8 = 8.3 Hz, JH10,H8 = 1.4 Hz, 1 H, 8-H), 8.61
(dd, JH ,P = 17.1 Hz, 1 H, Hi) ppm. 31P{1H} NMR (80.96 MHz,
4
CDCl3):i δ = 23.3 (s) ppm. FAB-MS: m/z = 579 [M]+.
Compounds 3a and 4a were obtained as violet solids by a similar
procedure, but with a 1:2 complex 1a/ diphosphane molar ratio.
H 5.3, N 1.8. IR: ν = 1544 (s, νC=N) cm–1. 1H NMR (200 MHz,
˜
CDCl3): δ = 1.27 (s, 9 H, tBu), 2.92, 3.73, 3.98 (s, 9 H, MeO), 5.49
[{Pd(2,3,4-{MeO}3 C6 HC{H}=N{2-O-5-tBuC6H3 })}2 (µ-
PPh2CH2PPh2)] (3a): Yield: 19 mg, 60 %. C65H68N2O8P2Pd2
(1280.03): calcd. C 60.9, H 5.3, N 2.2; found C 60.2, H 5.2, N 2.1.
(d, 4JH5,P = 3.4 Hz, 1 H, 5-H), 6.45 (d, 3JH10,H11 = 8.7 Hz, 1 H, 11-
3
4
H), 6.96 (dd, JH10,H11 = 8.7 Hz, JH8,H10 = 1.9 Hz, 1 H, 10-H),
4
4
7.05 (d, JH8,H10 = 1.9 Hz, 1 H, 8-H), 8.14 (d, JH ,P = 10.7 Hz, 1
1
IR: ν = 1544 (s, νC=N) cm–1. H NMR (200 MHz, CDCl3): δ = 1.32
i
˜
H, Hi) ppm. 31P{1H} NMR (80.96 MHz, CDCl3): δ = 34.2 (s) ppm.
(s, 9 H, tBu), 2.89, 3.70, 3.95 (s, 9 H, MeO), 5.39 (d, 4JH5,P = 4.3 Hz,
3
Compounds 2b–2f were prepared similarly as red or brown (2b)
solids.
1 H, 5-H), 6.46 (d, JH10,H11 = 9.2 Hz, 1 H, 11-H), 7.1 (m, 2 H, 10-
H, 8-H), 7.99 (d, JH ,P = 10.7 Hz, 1 H, Hi) ppm. 31P{1H} NMR
4
i
(80.96 MHz, CDCl3): δ = 25.6 (s) ppm.
[Pd{6-Me-2-CH2C6H3C(H)=N(2-OC6H4)}(PPh3)] (2b): Yield:
10 mg, 60%. C33H29NOPPd (592.98): calcd. C 66.8, H 4.9, N 2.4;
[{Pd(2,3,4-{MeO}3C6HC{H}=N{2-O-5-tBuC6H3})}2{µ-PPh2(CH2)
2PPh2}] (4a): Yield: 21 mg, 65 %. C66H70N2O8P2Pd2 (1294.06): calcd.
found C 66.5, H 4.7, N 2.3. IR: ν = 1581 (s, νC=N) cm–1. 1H NMR
˜
(200 MHz, CDCl3): δ = 2.55 (s, 3 H, Me), 2.96 (d, 3JCH ,P = 5.8 Hz,
C 61.3, H 5.4, N 2.1; found C 61.1, H 5.3, N 2.0. IR: ν = 1544 (s,
˜
2
2 H, -CH2-), 6.43 (t, 3JH10,H9 = 7.3 Hz, 1 H, 10-H), 6.52 (t, 4J
νC=N) cm–1. 1H NMR (200 MHz, CDCl3): δ = 1.30 (s, 9 H, tBu),
H5,CH2
3
= 4.4 Hz, 1 H, 2-H), 6.92 (m, 3 H), 7.09 (t, JH,H = 7.8 Hz, 1 H),
2.85, 3.72, 3.97 (s, 9 H, MeO), 5.38 (s, 1 H, 5-H), 6.51 (d, 3JH10,H11
=
4
3
4
8.69 (d, JH ,P
=
12.7 Hz,
1
H, Hi) ppm. 31P{1H} NMR 8.7 Hz, 1 H, 11-H), 7.01 (dd, JH10,H11 = 8.7 Hz, JH8,H10 = 1.9 Hz,
i
4
(80.96 MHz, CDCl3): δ = 33.4 (s) ppm.
1 H, 10-H), 7.09 (d, JH8,H10 = 1.9 Hz, 1 H, 11-H) ppm. 31P{1H}
NMR (80.96 MHz, CDCl3): δ = 35.0 (s) ppm.
[Pd{5-Me-2-CH2C6H3C(H)=N(2-OC6H4)}(PPh3)] (2c): Yield:
29 mg, 60%. C33H29NOPPd (592.98): calcd. C 66.8, H 4.9, N 2.4;
Compound 3b was obtained following a similar procedure as a brown
solid.
found C 66.4, H 4.8, N 2.3. IR: ν = 1581 (s, νC=N) cm–1. 1H NMR
˜
5416
www.eurjic.org
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2007, 5408–5418