FULL PAPER
[PTA–CH2CONH2]Br (1e): Yield 84%, white solid. 1H NMR
([D6]DMSO, 25 °C): δ = 8.01 (s, 1 H, NH2), 7.73 (s, 1 H, NH2), 31P{1H} NMR ([D6]DMSO): δ = –29.7 ppm. 13C{1H} NMR
4.17 (br. s, 1 H, CH2CϵCH), 4.11 (br. s, 2 H, CH2CϵCH) ppm.
5.28 and 5.06 (AB system, JA,B = 10.8 Hz, 4 H, NCH2N), 4.62 (s,
2 H, NCH2P), 4.55 (d, JH,H = 14 Hz, 1 H, NCH2N), 4.36 (d, JH,H
= 13.6 Hz, 1 H, NCH2N), 3.98–3.84 (m, 4 H, NCH2P), 3.66 (s, 2
(75.4 MHz, [D6]DMSO): δ = 84.9 (s, CϵCH), 78.5 (s, NCH2N),
70.3 (s, NCH2N), 55.9 (d, JP,C = 23.4 Hz, PCH2N), 51.3 (s,
CH2CϵCH), 47.9 (d, JP,C = 22 Hz, PCH2N) ppm. MALDI MS:
H, CH2CO) ppm. 31P{1H} NMR ([D6]DMSO): δ = –84.4 ppm. m/z (%) = 507 (18) [M + Br]+. IR: ν = 2118 cm–1 [ν(CϵC)].
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13C{1H} NMR (100.62 MHz, [D6]DMSO): δ = 165.15 (s, CO),
C9H15AuBrClN3P (508.53): calcd. C 21.26, H 2.97, N 8.26; found
80.20 (s, 2 C, NCH2N), 69.82 (s, NCH2N), 60.62 (s, CH2CO), 53.4 C 21.8, H 2.51, N 8.66. S25°C(H2O): 7.4 gL–1.
(d, JP,C = 32.7 Hz, PCH2N), 46.1 (d, JP,C = 20.2 Hz, PCH2N) ppm.
[AuCl(PTA–CH2CONH2)]Br (3e): Yield 76%, white solid. 1H
MALDI MS: m/z (%) = 215.3 (61) [M]+. IR: ν = 1696 cm–1
˜
NMR ([D6]DMSO 25 °C): δ = 8.09 (s, 1 H, NH2), 7.83 (s, 1 H,
NH2), 5.38 and 5.12 (AB system, JA,B = 11.2 Hz, 4 H, NCH2N),
4.99 (d, JH,H = 4 Hz, 2 H, NCH2P), 4.62–4.58 (m, 1 H, NCH2N),
4.4–4.32 (m, 4 H, NCH2N and NCH2P), 3.79 (s, 2 H, CH2CO)
ppm. 31P{1H} NMR ([D6]DMSO): δ = –34.1 ppm. 13C{1H} NMR
(75.4 MHz, [D6]DMSO): δ = 165.1 (s, CO), 80.1 (s, NCH2N), 69.7
(s, NCH2N), 60.5 (s, CH2CO), 53.7 (d, JP,C = 28 Hz, PCH2N), 46.5
(d, JP,C = 16.6 Hz, PCH2N) ppm. MALDI MS: m/z (%) = 449 (22)
[M]+. C8H16AuBrClN4OP (527.74): calcd. C 18.21, H 3.06, N
10.62; found C 18.83, H 3.12, N 10.41. S25°C(H2O): 243 gL–1.
[ν(C=O)]. C8H16BrN4OP (295.12): calcd. C 32.56, H 5.46, N 18.98;
found C 32.64, H 5.89, N 19.38. S25°C(H2O): 733 gL–1.
[PTA–CH2COOH]Br (1f): Yield 78%, white solid. 1H NMR ([D6]-
DMSO, 25 °C): δ = 5.09 (AB system, JA,B = 11.3 Hz, 4 H,
NCH2N), 4.7 (d, JH,H = 10.9 Hz, 1 H, NCH2N), 4.6 (d, JH,H
=
8 Hz, 2 H, NCH2P), 4.33 (d, JH,H = 13.4 Hz, 1 H, NCH2N), 3.88–
3.78 (m, 4 H, NCH2P), 3.5 (s, 1 H, CH2OOH) ppm. 31P{1H} NMR
([D6]DMSO): δ = –85.28 ppm. 13C{1H} NMR (100.62 MHz, [D6]-
DMSO): δ = 165.2 (s, CO), 79.5 (s, NCH2N), 71.2 (s, NCH2N),
61.7 (s, CH2COOH), 52.9 (d, JP,C = 31.2 Hz, PCH2N), 46.2 (d, JP,C
= 20.1 Hz, PCH2N) ppm. MALDI MS (%): m/z (%) = 216 (14.21)
[AuCl(PTA–CH2COOH)]Br (3f): Yield 78%, white solid. 1H NMR
([D6]DMSO, 25 °C): δ = 5.09–5.29 (AB system, JA,B = 11.3 Hz, 4
[M]+. IR: ν = 1684 cm–1 [ν(C=O)]. C8H16BrN4OP (296.1): calcd. C
˜
H, NCH2N), 4.78 (d, JH,H = 4 Hz, 2 H, NCH2P), 4.65 (d, JH,H
=
32.45, H 5.11, N 14.19; found C 32.72, H 5.4, N 14.47. S25°C(H2O):
582 gL–1.
10.7 Hz, 1 H, NCH2N), 4.31 (d, JH,H = 13.4 Hz, 1 H, NCH2N),
3.95 (d, JH,H = 8.7 Hz, 2 H, CH2CO), 3.75 (m, 4 H, NCH2P), 3.65
(s, 1 H, COOH) ppm. 31P{1H} NMR ([D6]DMSO): δ = –31.7 ppm.
13C{1H} NMR (75.4 MHz, [D6]DMSO): δ = 165.4 (s, CO), 79.6 (s,
Preparation of [PTA–R]Cl [R = –CH2CO2Me (2a)]: A solution of
RCl in acetone (2 mmol) was added to a solution of PTA (2 mmol,
0.314 g) in acetone (ca. 10 mL) heated at reflux. After stirring the
mixture for approximately 24 h, the white solids were isolated by
filtration, washed with acetone and diethyl ether and dried in air.
Yield 80%, white solid. 1H NMR ([D6]DMSO, 25 °C): δ = 5.26
and 5.13 (AB system, JA,B = 11.2 Hz, 4 H, NCH2N), 4.63 (d, JH,H
= 5.6 Hz, 2 H, NCH2P), 4.57–4.41 (m, 2 H, NCH2N), 4.04 (s, 2 H,
CH2COOMe), 3.98–3.87 (m, 4 H, NCH2P), 3.77 (s, 3 H, Me) ppm.
31P{1H} NMR ([D6]DMSO): δ = –84.4 ppm. 13C{1H} NMR
(75.4 MHz, [D6]DMSO): δ = 165 (s, CO), 79.8 (s, NCH2N), 70.2
(s, NCH2N), 59.9 (s, CH2CO), 53.8 (d, PCH2N), 53.5 (s, Me), 45.9
NCH2N), 71.7 (s, NCH2N), 61.0 (s, CH2COOH), 53.7 (d, JP,C
=
41 Hz, PCH2N), 46.5 (d, JP,C = 19 Hz, PCH2N) ppm. MALDI MS:
m/z (%) = 216 (14) [M]+, 447 (2) [M – H]+. IR: ν = 1684 cm–1
˜
[ν(C=O)]. C8H15AuBrClN3O2P (528.52): calcd. C 18.18, H 2.86, N
7.95; found C 18.3, H 2.7, N 7.14. S25°C(H2O): 180 gL–1.
Preparation of [AuCl(PTA–R)]Cl Complexes [R = –CH2CO2-
Me(4a), –CH2Ph(4b)]: [PTA–R]Cl (0.2 mmol) was added to a solu-
tion of [AuCl(tht)] (0.2 mmol; 0.0641 g) in acetone (ca. 10 mL). Af-
ter stirring the mixture for approximately 4 h, the solutions were
concentrated and the addition of Et2O precipitated the products,
which were isolated by filtration, dried in air as white solids and
recrystallised from MeOH/OEt2.
(d, PCH N) ppm. MALDI MS: m/z (%) = 229.8 (100) [M]+. IR: ν
˜
2
= 1745 cm–1 [ν(C=O)]. C9H17ClN3O2P (265.68): calcd. C 40.69, H
6.45, N 15.82; found C 40.18, H 6.99, N 15.47. S25°C(H2O):
2586 gL–1.
[AuCl(PTA–CH2CO2Me)]Cl (4a): Yield 86%, white solid. 1H
Preparation of [AuCl(PTA–R)]Br Complexes [R = –CH2CN (3c),
–CH2CϵCH (3d), –CH2CONH2 (3e), –CH2COOH (3f)]: [PTA–R]-
Br (0.2 mmol) was added to a solution of [AuCl(tht)] (0.2 mmol;
0.0641 g) in acetone (ca. 10 mL). After stirring the mixture for ap-
proximately 4 h, the solutions were concentrated and the addition
of Et2O precipitated the products, which were isolated by filtration
and dried in air as white solids.
NMR ([D6]DMSO, 25 °C): δ = 5.27 and 5.39 (AB system, JA,B
=
11.2 Hz, 4 H, NCH2N), 5.06 (d, JH,H = 5.6 Hz, 2 H, PCH2N),
4.59–4.52 (m, 2 H, NCH2N), 4.36–4.47 (m, 4 H, PCH2N +
CH2COOMe), 4.2 (s, 2 H, CH2Ph), 3.79 (s, 3 H) ppm. 31P{1H}
NMR ([D6]DMSO): δ = –31.7 ppm. 13C{1H} NMR (100.62 MHz,
[D6]DMSO): δ = 164.5 (s, CO), 80.75 (s, NCH2N), 69.08 (s,
NCH2N), 59.7 (s, CH2COOMe), 54.05 (d, JP,C = 27.6 Hz, PCH2N),
53.57 (s, COOMe), 48.22 (d, JP,C = 20.8 Hz, PCH2N) ppm.
[AuCl(PTA–CH2CN)]Br (3c): Yield 76%, white solid. 1H NMR
([D6]DMSO, 25 °C): δ = 5.28 and 5.19 (AB system, JH,H = 12 Hz,
4 H, NCH2N), 4.73 (s, 2 H, NCH2P), 4.65 (d, JH,H = 13.4 Hz, 1
H, NCH2N), 4.58 (s, 2 H, CH2CN), 4.38–4.46 (m, 1 H, NCH2N),
4.01–4.13 (m, 4 H, NCH2P) ppm. 31P{1H} NMR ([D6]DMSO): δ
= –75.5 ppm. 13C{1H} NMR (100.62 MHz, [D6]DMSO): δ = 111.3
(s, CN), 80.6 (s, NCH2N), 69.2 (s, NCH2N), 55.1 (d, JP,C = 26.1 Hz,
PCH2N), 48.3 (s, CH2CN), 46.5 (d, JP,C = 14 Hz, PCH2N) ppm.
MALDI MS: m/z (%) = 462 (11) [M]+. IR: ν = 1746 cm–1 [ν(CO)].
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C9H17AuCl2N3O2P (498.1): calcd. C 21.70, H 3.44, N 8.44; found
C 22.02, H 3.8, N 8.13. S25°C(H2O): 30 gL–1.
[AuCl(PTA–CH2Ph)]Cl (4b): Yield 97%, white solid. 1H NMR
([D6]DMSO 25 °C): δ = 7.55–7.61 (m, 5 H, Ph), 4.97 and 5.22 (AB
system, JA,B = 11.6 Hz, 4 H, NCH2N), 4.65 (d, JH,H = 5.6 Hz, 2
H, NCH2P), 4.57 (d, JH,H = 13.1 Hz, 1 H, NCH2N), 4.38–4.22 (m,
7 H, NCH2P + NCH2N + CH2Ph) ppm. 31P{1H} NMR ([D6]-
DMSO): δ = –30.4 ppm. 13C{1H} NMR (100.62 MHz, [D6]-
DMSO): δ = 135.5, 130.9, 129.6 (s, Ph), 78.9 (s, NCH2N), 69.1 (s,
NCH2N), 64.7 (s, CH2Ph), 52.3 (d, JP,C = 23 Hz, PCH2N), 47.9 (d,
JP,C = 23 Hz, PCH2N) ppm. MALDI MS: m/z (%) = 480.2 (100)
IR: ν = 1682 cm–1 [ν(CϵN)]. C8H14AuBrClN4P (509.52): calcd. C
˜
18.86, H 2.77, N 11.00; found C 19.35, H 2.73, N 11.38.
S25°C(H2O): 65.21 gL–1.
[AuCl(PTA–CH2CϵCH)]Br (3d): Yield 85%, white solid. 1H NMR
([D6]DMSO, 25 °C): δ = 5.03 and 5.12 (AB system, JH,H = 11.2 Hz,
4 H, NCH2N), 4.89 (d, JH,H = 5.3 Hz, 2 H, NCH2P), 4.66 (d, JH,H [M]+. C13H19AuCl2N3P (516.16): calcd. C 30.25, H 3.71, N 8.14;
= 13.4 Hz, 1 H, NCH2N), 4.28–4.43 (m, 5 H, NCH2N + NCH2P), found C 30.04, H 3.75, N 8.19.
Eur. J. Inorg. Chem. 2013, 2020–2030
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© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim