Inorganic Chemistry
Article
(
1
1
75.6 MHz, CDCl ): δ 166.5, 165.3, 147.6, 145.7, 143.0, 139.9, 133.9,
7.64−7.60 (1H, m), 7.57−7.52 (1H, m), 7.37−7.35 (1H, m), 7.24−7.22
3
C
3
30.9, 129.8, 128.6, 128.3, 126.1, 125.5, 125.2, 125.0, 117.6, 62.7, 46.3,
(1H, m), 7.10−7.08 (2H, m), 6.21 (1H, s), 4.55 (2H, q, J = 7.2 Hz),
HH
4.4. 1 Pt NMR (107.5 MHz, CDCl ): δ −3662. UV−vis (CHCl )
95
1.53 (3H, t, J = 7.2 Hz). C{ H} NMR (125.8 MHz, CDCl ): δ
3
13
1
3
Pt
3
HH
3
C
3
−1
−1
λmax (ε/dm mol cm ): 257 (28100), 293 (20100), 366 (9050) nm.
IR (thin film) νmax: 3048, 2976, 2918, 1715, 1597, 1578, 1543, 1514,
1
1
184.6, 183.1, 168.4, 163.8, 148.6, 144.5, 142.7, 139.1, 130.1, 128.8, 128.7,
126.3, 125.8, 124.1, 124.0, 123.3, 122.9, 121.6, 115.0, 114.9, 113.3, 100.9,
27.4, 26.1. 1 Pt NMR (107.5 MHz, CDCl ): δ −2693. UV−vis
95
466, 1451, 1397, 1375, 1348, 1292, 1271, 1248, 1233, 1194, 1130,
3
Pt
−
1
3
−1
−1
018, 758 cm .
(CHCl ) λ (ε/dm mol cm ): 253 (17700), 293 (12500), 370
3 max
Synthesis of [PtCl(L2)(DMSO)]. The title compound was synthesized
(5370), 400 (2930) nm. IR (thin film) νmax: 2934, 2851, 1724, 1624,
following the general procedure for splitting the platinum dimers using
Pt(L2)(μ-Cl)] (0.265 g, 0.249 mmol). The product obtained was a
yellow/green solid. Yield = 0.283 g (93%). Pt NMR (107.5 MHz,
1603, 1545, 1466, 1456, 1377, 1350, 1260, 1200, 1146, 1109, 1030, 735
−1
[
cm .
2
195
Synthesis of [Pt(L2)(acac)]. The title compound was synthesized
CDCl ): δ −3675.
following the general procedure for coordinating β-diketonates to
platinum complexes using [PtCl(L2)(DMSO)] (0.050 g, 0.077 mmol)
and sodium acetylacetonate monohydrate (0.094 g, 0.770 mmol). The
3
Pt
Synthesis of [PtCl(L3)(DMSO)]. The title compound was synthesized
following the general procedure for splitting the platinum dimers using
1
[
Pt(L3)(μ-Cl)] (0.151 g, 0.132 mmol). The product obtained was a
product obtained was a dark yellow solid. Yield = 0.046, (94%). H
2
1
95
3
brown/green solid. Yield = 0.156 g (91%). Pt NMR (107.5 MHz,
NMR (400 MHz, CDCl
J
3
): δ
H
9.51 (1H, d, JHH = 8.0 Hz), 7.95 (1H, d,
3
CDCl ): δ −3673.
HH = 8.0 Hz), 7.75−7.61 (3H, m), 7.55−7.42 (2H, m), 7.18−7.03 (2H,
m), 5.86 (1H, br s), 5.50 (1H, s), 1.97 (3H, s), 1.96 (3H, s), 1.50 (9H, s).
C{ H} NMR (125.8 MHz, CDCl ): δ 184.5, 183.1, 168.8, 165.3,
3 C
3
Pt
General Procedure for Coordinating β-Diketonates to Platinum
2
7
13
1
Complexes. On the basis of a modified literature methodology,
PtCl(L)(DMSO)] (1 equiv) was dissolved in 3-pentanone (5 mL), to
[
1
1
48.6, 144.8, 144.4, 139.2, 130.0, 129.0, 128.6, 126.2, 125.8, 124.0, 123.9,
which the β-diketonate (1−10 equiv) was added. The reaction was
stirred at room temperature for 16 h under dinitrogen. The solvent was
removed in vacuo, and the crude product was dissolved in dichloro-
methane (10 mL), filtered to remove any insoluble salts, and
concentrated to dryness in vacuo. The crude product was purified by
column chromatography (silica, dichloromethane) wherein elution of
the first yellow band with dichloromethane gave the desired product
195
23.4, 122.9, 112.9, 100.8, 51.9, 27.9, 27.3, 26.2. Pt NMR (107.5
3
−1
−1
MHz, CDCl ): δ −2779. UV−vis (CHCl ) λ (ε/dm mol cm ):
3
Pt
3
max
2
58 (28800), 297 (28300), 343 (9200), 360 (6800), 415 (3130) nm. IR
(
1
7
thin film) νmax: 3300, 3057, 2963, 2924, 2853, 1721, 1647, 1595, 1572,
549, 1516, 1456, 1393, 1366, 1302, 1263, 1219, 1161, 1092, 1028, 793,
−1
62, 733, 702 cm .
Synthesis of [Pt(L3)(acac)]. The title compound was synthesized
[
Pt(L)(acac)].
following the general procedure for coordinating β-diketonates to
platinum complexes using [PtCl(L3)(DMSO)] (0.050 g, 0.077 mmol)
and sodium acetylacetonate monohydrate (0.094 g, 0.770 mmol). The
Synthesis of [Pt(L1)(acac)]. The title compound was synthesized
following the general procedure for coordinating β-diketonates to
platinum complexes using [PtCl(L1)(DMSO)] (0.053 g, 0.091 mmol)
and sodium acetylacetonate monohydrate (0.111 g, 0.910 mmol). The
1
product obtained was a dark yellow solid. Yield = 0.046, (94%). H
3
NMR (400 MHz, CDCl ): δ 9.28 (1H, d, J = 8.8 Hz), 8.95 (1H, s),
3
H
HH
1
3
product obtained was a dark orange solid. Yield = 0.042 g (81%). H
7
.86 (1H, d, J = 8.0 Hz), 7.69−7.66 (2H, m), 7.49−7.45 (2H, m),
HH
3
4
NMR (400 MHz, CDCl ): δ 9.59 (1H, dd, J = 8.0 Hz, J = 0.4
3
H
HH
HH
7.36−7.31 (2H, m), 7.11−6.98 (4H, m), 6.80−6.76 (1H, m), 5.47 (1H,
3
4
s), 2.00 (3H, s), 1.81 (3H, s). 13C{ H} NMR (125.8 MHz, CDCl ): δ
1
Hz), 8.69 (1H, dd, J = 8.4 Hz, J = 1.2 Hz), 8.24 (1H, s), 7.81−
HH
HH
3
C
7
.75 (2H, m), 7.65−7.60 (2H, m), 7.29−7.25 (1H, m), 7.21−7.17 (1H,
184.6, 183.1, 168.4, 163.8, 148.6, 144.5, 142.7, 139.1, 130.1, 128.8, 128.7,
126.3, 125.8, 124.1, 124.0, 123.3, 122.9, 121.6, 121.5, 115.0, 114.9, 113.3,
3
m), 5.58 (1H, s), 4.56 (2H, q, J = 7.2 Hz), 2.06 (3H, s), 2.05 (3H, s),
HH
3
13
1
195
1
1
1
1
.52 (3H, t, J = 7.2 Hz). C{ H} NMR (75.6 MHz, CDCl ): δ
100.8, 27.4, 26.1. Pt NMR (107.5 MHz, CDCl ): δ −2769. UV−vis
HH
3
C
3
Pt
3
−1
−1
85.7, 184.2, 169.4, 165.7, 149.9, 145.7, 140.3, 137.4, 130.8, 130.0, 129.7,
27.7, 126.9, 125.4, 125.2, 125.1, 124.0, 118.1, 101.8, 62.3, 28.5, 27.2,
4.4. 1 Pt NMR (107.5 MHz, CDCl ): δ −2765. UV−vis (CHCl )
(CHCl ) λ (ε/dm mol cm ): 300 (14860), 342 (9840), 363
3 max
(4650), 442 (2170) nm. IR (thin film) νmax: 3262, 3063, 2963, 2924,
95
3
Pt
3
2853, 1672, 1655, 1582, 1547, 1522, 1508, 1456, 1404, 1373, 1308,
3
−1
−1
−1
λmax (ε/dm mol cm ): 253 (17500), 292 (13900), 300 (14400), 363
1260, 1211, 1157, 1090, 1015, 939, 864, 833, 800, 760, 729, 698 cm .
(
5570), 427 (3720) nm. IR (thin film) νmax: 3115, 3053, 2980, 2920,
Synthesis of [Pt(L4)(acac)]. [Pt(L1)(acac)] (0.029 g, 0.051 mmol)
was dissolved in acetone (5 mL) and potassium hydroxide (1 M, 5 mL)
and stirred for 16 h at room temperature under dinitrogen. The acetone
was removed in vacuo, and the solution was neutralized with
hydrochloric acid (1 M). The water was removed in vacuo, and the
solid was dissolved in methanol (5 mL) and filtered to remove inorganic
1
1
723, 1580, 1541, 1522, 1452, 1393, 1375, 1298, 1267, 1238, 1196,
146, 1028, 762 cm .
Synthesis of [Pt(L1)(hmacac)]. The title compound was synthesized
−
1
following the general procedure for coordinating β-diketonates to
platinum complexes using [PtCl(L1)(DMSO)] (0.023 g, 0.039 mmol)
and sodium 2,2,6,6-tetramethyl-3,5-heptanedionate (hmacac) mono-
1
salts. Yield = 0.024 g (87%). H NMR (400 MHz, CD OD): δ 9.58
3
H
1
3
3
4
hydrate (0.009 g, 0.043 mmol). Yield = 0.024 g (93%). H NMR (400
(1H, d, J = 9.2 Hz), 8.30 (1H, dd, J = 8.4 Hz, J = 1.6 Hz), 7.93
HH HH HH
3
3
MHz, CDCl ): δ 9.70 (1H, d, J = 9.2 Hz), 8.71 (1H, dd, J = 8.4
(1H, s), 7.73−7.69 (1H, m), 7.65−7.62 (1H, m), 7.58−7.53 (2H, m),
13 1
3
H
HH
HH
4
3
Hz, J = 0.8 Hz), 8.26 (1H, s), 7.88 (1H, dd (with satellites), J
=
7.13−7.07 (2H, m), 5.48 (1H, s), 2.86 (3H, s), 1.81 (3H, s). C{ H}
NMR (125.8 MHz, CD OD): δ 185.7, 183.9, 172.8, 169.9, 150.2,
HH
HH
4
7
7
.6 Hz, J = 0.8 Hz), 7.81−7.77 (1H, m) 7.67−7.61 (2H, m), 7.32−
HH
3
C
3
.28 (1H, m), 7.23−7.19 (1H, m), 5.94 (1H, s), 4.58 (2H, q, J = 7.2
149.6, 146.5, 139.1, 130.1, 129.5, 128.5, 127.4, 126.3, 126.0, 124.7, 124.4,
HH
3
13
1
195
Hz), 1.54 (3H, t, J = 7.2 Hz), 1.35 (9H, s), 1.30 (9H, s). C{ H}
123.4, 113.2, 101.0, 26.9, 25.7. Pt NMR (107.5 MHz, CD OD): δ
HH
3
Pt
−
NMR (75.6 MHz, CDCl ): δ 195.7, 193.9, 169.5, 165.8, 150.0, 145.8,
−2781. ES MS found m/z = 541.06 for [M − H] . UV−vis (MeOH)
3 −1 −1
3
C
1
1
41.1, 137.4, 131.0, 130.5, 129.7, 127.7, 127.5, 125.4, 125.1, 125.0, 123.9,
λ
(ε/dm mol cm ): 282 (4990), 334 (1850), 348 (1940), 382
max
18.1, 92.8, 62.4, 42.3, 41.1, 28.8, 28.6, 14.4. 195Pt NMR (107.5 MHz,
(1360) nm. IR (thin film) νmax: 3379, 2963, 2918, 2849, 1659, 1576,
3
−1
−1
−1
CDCl ): δ −2733. UV−vis (CHCl ) λ (ε/dm mol cm ): 253
1539, 1520, 1454, 1393, 1360, 1337, 1277, 1024, 764 cm .
3
Pt
3
max
(
(
18700), 291 (12300), 301 (13000), 357 (5220), 437 (3610) nm. IR
thin film) νmax: 3117, 3057, 2961, 2924, 2855, 1724, 1601, 1584, 1559,
Synthesis of [Pt(L1)(8-Q)]. On the basis of a modified literature
2
8
methodology, [PtCl(L1)(DMSO)] (0.038 g, 0.065 mmol), Na CO
2 3
1
1
549, 1530, 1497, 1462, 1452, 1391, 1357, 1360, 1263, 1238, 1225,
194, 1144, 1026, 791, 760 cm .
Synthesis of [Pt(L1)(hfacac)]. The title compound was synthesized
(0.008 g, 0.072 mmol), and 8-hydroxyquinoline (0.010 g, 0.072 mmol)
were heated to 100 °C with stirring under dinitrogen in 2-
methoxyethanol (5 mL) for 24 h. The product was purified by column
chromatography (silica, dichloromethane) and then eluted as the first
red band with dichloromethane and dried to yield a dark red solid. Yield
−1
following the general procedure for coordinating β-diketonates to
platinum complexes using [PtCl(L1)(DMSO)] (0.022 g, 0.057 mmol),
Na CO (0.007 g, 0.063 mmol), and hexafluoroacetylacetone (0.013 g,
1
3
= 0.035 g (88%). H NMR (400 MHz, CDCl ): δ 9.93 (1H, d, J =
2
3
3
H
HH
3
3
0
.063 mmol). The product obtained was a yellow solid. Yield = 0.036 g,
8.8 Hz), 9.18 (1H, d (with satellites J = 44 Hz), J = 5.2 Hz), 8.66
HPt HH
1
3
3
4
3
4
(
92%). H NMR (400 MHz, CDCl ): δ 8.97 (1H, dd, J = 9.2 Hz,
(1H, dd, J = 8.4 Hz, J = 0.8 Hz), 8.28 (1H, dd, J = 8.0 Hz, J
HH HH HH HH
3
H
HH
4
3
4
JHH = 0.8 Hz), 8.75 (1H, dd, J = 8.4 Hz, J = 1.2 Hz), 7.95 (1H, s),
= 0.8 Hz), 8.23 (1H, s), 7.94−7.91 (1H, m), 7.67−7.63 (2H, m), 7.56−
HH
HH
C
Inorg. Chem. XXXX, XXX, XXX−XXX