Inorganic Chemistry
Article
3
4
5
phenyl-H3′/H5′), 7.33 (t, 2H, 3J
,
H2’/H6’ H3′/H5′ = 8.0 Hz, phenyl-H2’/
1H, JH6,H5= 5.5 Hz, JH6,H4 = 1.5 Hz, JH6,H3= 0.6 Hz, py-H6), 8.23
3
3
4
H6’), 7.04 (t, 1H, JH4′,H3′/H5′ = 7.4 Hz, phenyl-H4’), 2.45 (s, 3H,
CH3) ppm; 13C NMR (125.76 MHz, DMSO-d6): δ 172.68 (C-S),
159.30 (CN), 157.57 (py-C2), 147.20 (py-C6), 141.09 (phenyl-
C1’), 140.21 (py-C4), 128.72 (phenyl-C3′/C5′), 126.91 (py-C5),
125.57 (py-C3), 123.21 (phenyl-C4’), 119.89 (phenyl-C2’′/C6′),
13.61 (CH3) ppm; Anal. Calcd for C14H13N7PdS (417.79 g mol−1):
C, 40.25; H, 3.14; N, 23.47; S, 7.68. Found (%): C, 40.29; H, 3.33; N,
23.16; S, 7.63.
(dt, 1H, JH4,H3/H5 = 7.9 Hz, JH4,H6 = 1.6 Hz, py-H4), 7.92 (d, 1H,
3JH3,H4 = 7.4 Hz, py-H3), 7.72 (ddd, 1H, 3JH5,H4 = 7.7 Hz, 3JH5,H6 = 5.6
4
3
Hz, JH5,H3 = 1.3 Hz, py-H5), 7.60 (d, 2H, JH3′/H5′,H2′/H6′ = 7.7 Hz,
3
phenyl-H3′/H5′), 7.34 (t, 2H, JH2′/H6′,H3′/H5′ = 8.0 Hz, phenyl-H2′/
H6′), 7.05 (t, 1H, 3JH4′,H3′/H5′ = 7.4 Hz, phenyl-H4′), 4.32 (q, 2H, 3J =
7.1 Hz, CH2CH3), 2.56 (s, 3H, CH3), 1.31 (t, 3H, 3J = 7.1 Hz,
CH2CH3) ppm. 13C NMR (125.76 MHz, DMSO-d6): δ 175.24 (C-S),
161.21 (CN), 159.42 (COOEt), 158.72 (py-C2), 148.70 (py-C6),
140.85 (phenyl-C1′), 140.14 (py-C4), 138.17 (q, 2JC,F= 37.8 Hz,
triazolate-C4), 136.74 (q, 3JC,F= 0.9 Hz, triazolate-C5), 128.67
(phenyl-C3′/C5′), 127.51 (py-C5), 126.53 (py-C3), 123.34
(phenyl-C4′), 121.14 (q, 1JC,F= 268.2 Hz, CF3), 120.07 (phenyl-
[Pt(N3)(L)] (13). In a round-bottom flask, [PtCl(L)] (80 mg, 0.16
mmol) was dissolved in acetone (40 mL) with heating to 75 °C. To
the clear dark red solution was then added sodium azide (259 mg,
3.98 mmol) in water (10 mL), and heating was continued for 6 h. The
volume of resulting solution was decreased to about 15 mL, upon
which a red precipitate formed, which was collected, washed with
water (3 × 10 mL), and dried under vacuum for 1 day. Yield: 88% (72
mg, 0.14 mmol). IR (ATR): = 3279, 3137, 3086, 2061, 1600, 1550,
C2′/C6′), 61.80 (CH2CH3), 13.95 (CH3), 13.76 (CH2CH3) ppm. 19
F
NMR (470.59 MHz, DMSO-d6): δ −58.71 (CF3) ppm. 195Pt NMR
(107.51 MHz, DMSO-d6): δ −3108 ppm. Anal. Calcd for
C20H18F3N7O2PtS (672.55 g mol−1): C, 35.72; H, 2.70; N, 14.58;
S, 4.77. Found: C, 35.78; H, 2.55; N, 14.24; S, 4.60.
1493, 1458, 1434, 1317, 1252, 1154, 1073, 755, 735 cm−1. H NMR
1
[Pd(triazolateCOOCH3,COOCH3-N2)(L)] (18). In a large glass vial,
[Pd(N3)(L)] (40 mg, 0.10 mmol) was suspended in acetone (16
mL) at room temperature. Then, dimethyl acetylenedicarboxylate (20
μL, 23.1 mg, 0.16 mmol) was added to the orange suspension and
stirring was continued at room temperature for 15 h. The resulting
orange precipitate was filtered off, washed with n-hexane (5 × 5 mL),
and dried under vacuum for 1 day. Yield: 70% (39 mg, 0.07 mmol).
IR (ATR): 3308, 3092, 1730, 1709, 1602, 1553, 1502, 1460, 1437,
(500.13 MHz, DMSO-d6): δ 10.30 (s, 1H, NH-phenyl), 8.44 (ddd,
3
4
5
1H, JH6,H5= 5.4 Hz, JH6,H4 = 1.5 Hz, JH6,H3= 0.7 Hz, py-H6), 8.21
3
4
(dt, 1H, JH4,H3/H5 = 7.9 Hz, JH4,H6 = 1.6 Hz, py-H4), 7.87 (d, 1H,
3JH3,H4 = 8.0 Hz, py-H3), 7.69 (ddd, 1H, 3JH5,H4 = 7.7 Hz, 3JH5,H6 = 5.5
4
3
Hz, JH5,H3 = 1.3 Hz, py-H5), 7.62 (d, 2H, JH3′/H5′,H2′/H6′ = 7.7 Hz,
3
phenyl-H3′/H5′), 7.35 (t, 2H, JH2′/H6′,H3′/H5′ = 8.0 Hz, phenyl-H2′/
3
H6′), 7.05 (t, 1H, JH4′,H3′/H5′ = 7.4 Hz, phenyl-H4′), 2.45 (s, 3H,
CH3) ppm. 13C NMR (125.76 MHz, DMSO-d6): δ 175.42 (C-S),
159.57 (CN), 158.72 (py-C2), 146.02 (py-C6), 140.72 (phenyl-
C1′), 140.24 (py-C4), 128.68 (phenyl-C3′/C5′), 127.65 (py-C5),
126.24 (py-C3), 123.39 (phenyl-C4′), 120.14 (phenyl-C2′/C6′),
13.64 (CH3) ppm. 195Pt NMR (107.51 MHz, DMSO-d6): δ −3101
ppm. Anal. Calcd for C14H13N7PtS (506.45 g mol−1): C, 33.20; H,
2.59; N, 19.36; S, 6.33. Found: C, 33.38; H, 2.84; N, 19.34; S, 6.29.
[Pd(triazolateCF3,COOEt-N2)(L)] (17). In a large glass vial, [Pd(N3)-
(L)] (35 mg, 0.08 mmol) was suspended in acetone (20 mL) at room
temperature. Then, 4,4,4-trifluoro-2-butynoic acid ethyl ester (30 μL,
38.1 mg, 0.23 mmol) was added to the orange suspension and stirring
was continued at room temperature until the solution became clear,
which took about 3 h. The resulting clear dark orange solution was
then evaporated to dryness. The orange solid obtained was washed
with n-hexane (5 × 5 mL) and dried under vacuum for 1 day. Yield:
75% (37 mg, 0.06 mmol). IR (ATR): 3333, 1709, 1601, 1544, 1510,
1466, 1438, 1310, 1191, 1134, 1060, 763, 746 cm−1. 1H NMR
(500.13 MHz, DMSO-d6): δ 10.22 (s, 1H, NH-phenyl), 8.91 (dd, 1H,
3JH6,H5= 5.4 Hz, 4JH6,H4= 1.1 Hz, py-H6), 8.24 (dt, 1H, 3JH4,H3/H5 = 7.9
1396, 1294, 1159, 1090, 828, 800, 770, 756 cm−1; H NMR (500.13
1
MHz, DMSO-d64): δ 10.18 (s, 1H, NH-phenyl), 8.91 (ddd, 1H,
3JH6,H5= 5.4 Hz, JH6,H4 = 1.6 Hz, JH6,H3= 0.5 Hz, py-H6), 8.24 (dt,
5
1H, 3JH4,H3/H5 = 7.9 Hz, 4JH4,H6 = 1.6 Hz, py-H4), 7.97 (d, 1H, 3JH3,H4
3
3
= 7.5 Hz, py-H3), 7.69 (ddd, 1H, JH5,H4 = 7.7 Hz, JH5,H6 = 5.4 Hz,
4JH5,H3 = 1.3 Hz, py-H5), 7.58 (d, 2H, JH3′/H5′,H2′/H6′ = 7.7 Hz,
3
3
phenyl-H3′/H5′), 7.32 (t, 2H, JH2′/H6′,H3′/H5′ = 8.0 Hz, phenyl-H2′/
3
H6′), 7.04 (t, 1H, JH4′,H3′/H5′ = 7.4 Hz, phenyl-H4′), 3.81 (s, 6H,
COOCH3), 2.52 (s, 3H, CH3) ppm. 13C NMR (125.76 MHz,
DMSO-d6): δ 173.21 (C-S), 161.99 (COOCH3), 160.47 (CN),
157.78 (py-C2), 149.47 (py-C6), 141.24 (phenyl-C1′), 140.17 (py-
C4), 139.40 (triazolate-C4/C5), 128.80 (phenyl-C3′/C5′), 12.89
(py-C5), 125.92 (py-C3), 123.31 (phenyl-C4′), 120.04 (phenyl-C2′/
C6′), 52.05 (COOCH3), 14.01 (CH3) ppm. MS (ESI+, CH3CN):
416.0149 [M − triazolate + CH3CN]+, 560.0325 [M + H]+, 582.0143
[M + Na]+, 936.0145 [2M − triazolate]+, 1143.0409 [2M + Na]+.
Anal. Calcd for C20H19N7O4PdS (559.90 g mol−1): C, 42.90; H, 3.42;
N, 17.51; S, 5.73. Found: C, 42.85; H, 3.79; N, 17.58; S, 5.62.
[Pt(triazolateCOOCH3,COOCH3-N1)(L)] (22). In a large glass vial,
[Pt(N3)(L)] (30 mg, 0.06 mmol) was suspended in acetone (15
mL) at room temperature. Then, dimethyl acetylenedicarboxylate (30
μL, 34.7 mg, 0.24 mmol) was added to the red suspension and stirring
was continued at room temperature for 11 days. Then the volume of
solution was decreased to about 7 mL and the resulting orange
precipitate was filtered off, washed with n-hexane (3 × 5 mL), and
dried under vacuum for 1 day. Yield: 60% (23 mg, 0.04 mmol). IR
(ATR): 3013, 1730, 1728, 1560, 1512, 1461, 1440, 1322, 1259, 1202,
4
3
Hz, JH4,H6 = 1.6 Hz, py-H4), 8.00 (d, 1H, JH3,H4 = 8.0 Hz, py-H3),
7.72 (ddd, 1H, 3JH5,H4 = 7.7 Hz, 3JH5,H6 = 5.5 Hz, 4JH5,H3 = 1.3 Hz, py-
H5), 7.60 (d, 2H, 3JH3′/H5′,H2′/H6′ = 7.8 Hz, phenyl-H3′/H5′), 7.33 (t,
3
2H, JH2′/H6′,H3′/H5′ = 7.7 Hz, phenyl-H2′/H6′), 7.05 (t, 1H,
3JH4′,H3′/H5′ = 7.4 Hz, phenyl-H4′), 4.31 (q, 2H, 3J = 7.1 Hz,
3
CH2CH3), 2.53 (s, 3H, CH3), 1.30 (t, 3H, J = 7.1 Hz, CH2CH3)
ppm. 13C NMR (125.76 MHz, DMSO-d6): δ 172.89 (C-S), 160.69
(CN), 159.70 (COOEt), 157.76 (py-C2), 149.36 (py-C6), 141.30
(phenyl-C1′), 140.13 (py-C4), 137.88 (triazolate-C4), 136.64
(triazolate-C5), 128.77 (phenyl-C3′/C5′), 126.91 (py-C5), 125.98
(py-C3), 123.26 (phenyl-C4′), 121.41 (q, 1JC,F= 268.1 Hz, CF3),
119.88 (phenyl-C2′/C6′), 60.74 (CH2CH3), 14.00 (CH3), 13.99
(CH2CH3) ppm. 19F NMR (470.59 MHz, DMSO-d6): δ −58.58
(CF3) ppm. Anal. Calcd for C20H18F3N7O2PdS (583.89 g mol−1): C,
41.14; H, 3.11; N, 16.79 S, 5.49. Found: C, 41.23; H, 3.09; N, 16.21;
S, 5.43.
1154, 1108, 1037, 758 cm−1. H NMR (400.40 MHz, DMSO-d6): δ
10.42 (s, 1H, NH-C6H5), 8.28 (t, 1H, JH4,H3/H5= 8.4 Hz, py-H4),
1
3
8.00−7.96 (m, 2H, py-H3, py-H6), 7.69−7.64 (m, 3H, py-H5,
3
phenyl-H3′/H5′), 7.36 (t, 2H, JH2′/H6′,H3′/H5′ = 7.7 Hz, phenyl-H2′/
3
H6′), 7.06 (t, 1H, JH4′,H3′/H5′ = 7.6 Hz, phenyl-H4′), 3.84 (s, 3H,
triazolate-C5-COOCH3), 3.80 (s, 3H, triazolate-C4-COOCH3), 2.61
(s, 3H, CH3) ppm. No 13C and 195Pt NMR spectra could be recorded
due to the low solubility of the compound in common solvents. Anal.
Calcd for C20H19N7O4PtS (648.56 g mol−1): C, 37.04; H, 2.95; N,
15.12; S, 4.94. Found (%): C, 36.95; H, 3.03; N, 15.22; S, 4.94.
[Pt(triazolateCOOCH3,COOCH3-N2)(L)] (25). A suspension of [Pt-
(triazolateCOOCH3,COOCH3-N1)(L)] (approximately 10 mg) in
DMSO-d6 was kept in an NMR tube at room temperature for 7
days, during which time the light orange suspension turned to a clear
[Pt(triazolateCF3,COOEt-N2)(L)] (21). In a large glass vial, [Pt(N3)(L)]
(25 mg, 0.05 mmol) was suspended in acetone (20 mL) at room
temperature. Then, 4,4,4-trifluoro-2-butynoic acid ethyl ester (10 μL,
12.7 mg, 0.07 mmol) was added to the red suspension and stirring
was continued at room temperature for 2 d. The resulting clear red
solution was evaporated to dryness. The red solid obtained was
washed with n-hexane (5 × 5 mL) and dried under vacuum for 1 day.
Yield: 80% (25 mg, 0.04 mmol). IR (ATR): 3336, 1710, 1546, 1499,
1467, 1437, 1311, 1192, 1135, 1061, 760, 747 cm−1. 1H NMR
(500.13 MHz, DMSO-d6): δ 10.30 (s, 1H, NH-phenyl), 9.21 (ddd,
1
dark red solution. H NMR (500.13 MHz, DMSO-d6): δ 10.30 (s,
3
4
1H, NH-C6H5), 9.24 (ddd, 1H, JH6,H5= 5.6 Hz, JH6,H4 = 1.5 Hz,
5JH6,H3= 0.6 Hz, py-H6), 8.25 (dt, 1H, JH3,H4 = 7.9 Hz, JH3,H5 = 1.6
3
4
J
Inorg. Chem. XXXX, XXX, XXX−XXX