Dalton Transactions
Paper
8.31 (d, 1H, JH–H = 7.9 Hz; H3), 7.99 (td, 1H, JH–H = 7.8, 1.7 Hz; H4),
[(PPh3)Au(μ-pbi)Pt(Me)(DMSO)][PF6] (4-PF6). A solution of
7.69 (m, 1H, JH–H = 9.3, 7.0, 2.1 Hz; H6′), 7.51 (m, 2H; H5 + H3′), [AuCl(PPh3)] (241.7 mg, 0.5 mmol) and AgPF6 (126.4 mg,
7.21 (m, 2H, JH–H = 7.4, 1.5 Hz; H4′, H5′).
0.5 mmol) in dichloromethane (30 mL) was stirred in the dark
[PdCl2(pbiH)] (1). An ethanol solution (10 mL) of pbiH until AgCl precipitation was completed. Then, the filtered solu-
(150 mg, 0.77 mmol) was added to a solution of K2PdCl4 tion was added to a solution of 3 (241.7 mg, 0.5 mmol) in the
(250 mg, 0.77 mmol) in the same solvent (30 mL). The result- same solvent (20 mL). The mixture was stirred in the dark for
ing mixture was stirred in the dark for 6 h at 78 °C. The solid 4 h at room temperature. Afterwards the solution was filtered
which formed was filtered off, washed with water, EtOH and and concentrated to a small volume; addition of diethyl ether
Et2O and dried under vacuum. Yield 87%. Mp > 400 °C. Anal. gave a yellow solid which was filtered off and vacuum dried to
Calc. for C12H9N3Cl2Pd: C, 38.69; H, 2.43; N, 11.28%. Found: give the analytical sample. Yield 71%. Mp: 163 °C (dec.). Anal.
C, 38.39; H, 2.50; N, 11.09%. Selected IR bands (νmax/cm−1
,
Calcd for C33H32AuF6N3OP2PtS: C, 36.47; H, 2.97; N, 3.87%.
Nujol): 1612, 1588, 1567, 1481, 1459, 1446, 341 and 324 Found: C, 36.19; H, 3.01; N, 3.68%. Selected IR bands
1
ν(Pd–Cl); H NMR (300 MHz, DMSO-d6): δ 14.86 (broad s, 1H; (νmax/cm−1, Nujol): 1609, 1019 (PPh3), 840 (PF6), 748, 712.
NH), 9.09 (d, 1H, JH–H = 5.6 Hz; H6), 8.68 (d, 1H, JH–H = 8.1 Hz; 1H NMR (400 MHz, CDCl3): δ 9.64 (d, 1H, JH–H = 5.6, Hz; H6),
H3), 8.40 (td, 1H, JH–H = 7.8, 1.6 Hz; H4), 8.32 (d, 1H, JH–H
=
8.82 (broad d, 1H; H3), 7.95 (t, 1H, JH–H = 8.0 Hz; H4), 7.89
7.0 Hz; H6′), 7.81 (ddd, 1H, JH–H = 7.4, 5.7, 1.6 Hz; H5), 7.76 (d, 1H, JH–H = 8.0 Hz; H3′), 7.75 (d, 1H, JH–H = 8.0 Hz; H6′),
(d, 1H, JH–H = 8.3 Hz; H3′), 7.48 (td, 1H, JH–H = 7.0, 1.3 Hz; H5′), 7.56–7.40 (m, 16H; H5 + H-PPh3), 7.26 (t, 2H, JH–H = 7.6 Hz,
7.40 (td, 1H, JH–H = 8.4, 1.3 Hz; H4′).
H4′/H5′), 7.19 (t, JH–H = 7.8 Hz, H5′/H4′), 3.42 (s, 6H, JPt–H
3
[PtCl2(pbiH)] (2). A dichloromethane solution (10 mL) of 30.4 Hz; Me-DMSO), 1.20 (s, 3H, 2JPt–H = 73.2 Hz; Me). 1H NMR
pbiH (97.6 mg, 0.5 mmol) was added to a solution of (400 MHz, CD3CN): δ 9.70 (d, 1H, JH–H = 5.6, Hz; H6), 8.86
cis-[PtCl2(DMSO)2] (211 mg, 0.5 mmol) in the same solvent (broad d, 1H; H3), 7.99 (t, 1H, JH–H = 8.0 Hz; H4), 7.91 (d, 1H,
(30 mL). The mixture was stirred in the dark for 3 h at room JH–H = 8.0 Hz; H3′), 7.84 (broad d, 1H, JH–H = 6.8 Hz; H6′), 7.81
temperature. The yellow solid which formed was filtered off (dt, 1H, JH–H = 8.0, 1.6 Hz; H5), 7.70–7.63 (m, 15H; H-PPh3),
and dried under vacuum. Yield 81%. Mp 239 °C (dec.). Anal. 7.23 (m, 2H, JH–H = 8.0, 6.8 Hz, H4′, H5′), 3.40 (s, 6H, 3JPt–H 34.4
2
Calc. for C12H9N3Cl2Pt: C, 31.25; H, 1.97; N, 9.11%. Found: Hz; Me-DMSO), 1.12 (s, 3H, JPt–H = 78.4 Hz; Me). 31P NMR
C, 31.19; H, 1.85; N, 9.02%. Selected IR bands (νmax/cm−1
,
(161.9 MHz, CDCl3): δ 33.2 (s, PPh3); −144.1 (hept, PF6).
1
Nujol): 1614, 1590, 1496, 1483, 344 and 328 ν(Pt–Cl); H NMR 31P NMR (161.9 MHz, CD3CN): δ 30.9 (s, PPh3); −144.6
(300 MHz, DMSO-d6): δ 13.53 (broad s, 1H; NH), 9.46 (d, 1H, (hept, PF6).
JH–H = 5.7 Hz; H6), 8.78 (d, 1H, JH–H = 8.4 Hz; H3), 8.44 (t, 1H,
[(TPA)Au(μ-pbi)Pt(Me)(DMSO)]Cl (5-Cl). An acetone solu-
JH–H = 7.8 Hz; H4), 8.31 (d, 1H, JH–H = 7.8 Hz; H6′), 7.83–7.78 tion (20 mL) of [Pt(pbi)(Me)(DMSO)] (154.6 mg, 0.32 mmol)
(m, 2H; H3′ + H5), 7.51 (pseudo t, 1H, JH–H = 7.5, 7.2 Hz; H5′), was added to
suspension of [Au(TPA)Cl] (125.2 mg,
7.42 (pseudo t, 1H, JH–H = 8.1, 7.2 Hz; H4′).
0.32 mmol) in the same solvent (30 mL). The mixture was
a
[Pt(pbi)(Me)(DMSO)] (3). A dichloromethane solution stirred for 24 h at room temperature in the dark. Afterwards
(10 mL) of pbiH (97.6 mg, 0.5 mmol) was added to a solution the solution was filtered and concentrated to a small volume;
of cis-[PtMe2(DMSO)2] (190.7 mg, 0.5 mmol) in the same addition of diethyl ether afforded a beige solid that was
solvent (30 mL). The mixture was stirred in the dark for 24 h at filtered off and vacuum dried to give the analytical sample.
room temperature. Afterwards the solution was filtered and Yield 57%. Mp: 165 °C. Anal. Calcd for C21H29AuClN6OPPtS:
concentrated to a small volume; addition of diethyl ether C, 28.92; H, 3.35; N, 9.64%. Found: C, 29.02; H, 3.14;
afforded a yellow solid that was filtered off and vacuum dried N, 9.55%. Selected IR bands (νmax/cm−1, Nujol): 1609, 1279,
to give the analytical sample. Yield 72%. Mp 393 °C. Anal. 1151, 1098, 1014, 948, 741. 1H NMR (400 MHz, acetone-d6):
Calcd for C15H18N3OPtS: C, 37.34; H, 3.55, N, 8.71%. Found: 9.67 (d, 1H, JH–H = 6.0, 3JPt–H = 19.2 Hz; H6), 8.33 (d, 1H, JH–H
=
C, 37.10; H, 3.55; N, 8.82%. Selected IR bands (νmax/cm−1
,
7.6 Hz, H3), 8.17 (t, 1H, JH–H = 8.0, 7.2 Hz, H4), 7.83 (dd, 1H,
1
Nujol): 1613, 1567, 1167, 1117, 888, 740. H NMR (400 MHz, JH–H = 7.2, 1.6 Hz, H3′), 7.64 (dd, 1H, JH–H = 6.0, 2.4 Hz, H6′),
CD2Cl2): δ 9.50 (d, 1H, JH–H = 6.0, JPt–H = 21.2 Hz; H6), 8.24 7.56 (t, 1H, JH–H = 6.0, Hz, H5), 7.08 (m, 2H, H4′, H5′), 4.68
3
(d, 1H, JH–H = 7.6 Hz; H3), 7.89 (t, 1H, JH–H = 7.6 Hz; H4), 7.77 (d, 3H, JAB = 12.4 Hz, 3 N–CHAHB–N), 4.56 (d, 3H, JAB = 12.4 Hz,
(d, 1H, JH–H = 8.0 Hz; H3′), 7.61 (d, 1H, JH–H = 7.6 Hz; H6′), 7.30 3 N–CHAHB–N), 4.45 (s, 6H, 3 N–CH2–P), 3.54 (s, 6H, JPt–H
=
3
(t, broad, 1H, JH–H = 6.8 Hz; H5), 7.05 (m, 2H, JH–H = 7.6 Hz, 32.8 Hz, CH3-DMSO), 1.26 (s, 3H, JPt–H = 79.2 Hz, CH3).
2
H4′, H5′), 3.34 (s, 6H, JPt–H = 32.4 Hz; Me-DMSO), 1.16 (s, 3H, 31P NMR (161.9 MHz, acetone-d6): δ −52.9 (s, TPA).
3
2JPt–H = 78.8 Hz; Me). 1H NMR (400 MHz, CD3CN): δ 9.60
3
UV-visible spectrophotometric studies
(d, 1H, JH–H = 5.2, JPt–H = 20.4 Hz; H6), 8.28 (d, 1H, JH–H
=
7.6 Hz; H3), 8.07 (td, 1H, JH–H = 8.0, 1.6 Hz; H4), 7.85 (dd, 1H, The electronic spectra were recorded by diluting small
JH–H = 7.2, 2.4 Hz; H3′), 7.65 (dd, 1H, JH–H = 6.0, 2.0 Hz; H6′), amounts of freshly prepared concentrated solutions of the
7.49 (ddd, 1H, JH–H = 7.6, 6.0, 1.6 Hz; H5), 7.12 (m, 2H, JH–H
=
individual complexes in DMSO in phosphate buffer at pH 7.4
7.2, 1.6 Hz, H4′, H5′), 3.41 (s, 6H, JPt–H = 32.8 Hz; Me-DMSO), or in ammonium acetate at pH 6.8 (spectral profiles shown in
3
2
1.23 (s, 3H, JPt–H = 80.4 Hz; Me). Assignments based on Fig. S5†). The concentration of each compound in the final
2D-COSY and NOESY spectra.
sample was 10−4 M or 3 × 10−5 M.
This journal is © The Royal Society of Chemistry 2015
Dalton Trans.