Inorganic Chemistry
Article
any undissolved solid was filtered off. The filtrate was evaporated
under reduced pressure. The crude product was washed with
chloroform, acetone, and absolute ethanol, and subsequent recrystal-
lization by diffusion of diethyl ether vapor into the methanol−
acetonitrile solution of 1 gave the product as a dark-brown solid (182
883.1 ([M − OTf]+). Elem anal. Calcd for C38H37F6N5O6PtS2·2H2O:
C, 42.70; H, 3.87; N, 6.55. Found: C, 42.59; H, 3.95; N, 6.66.
[Pt{tpy(C6H4CH2NMe3-4)-4′}{CCC6H4(CH2NH2)-4}](OTf)2 (6).
The procedure was similar to that for complex 3 except that 4-
ethynylbenzylamine (145 mg, 1.0 mmol) was used instead of 4-
ethynylbenzoic acid. The product was obtained as a dark-brown solid
1
mg, 0.25 mmol, 75%). H NMR (400 MHz, [D6]DMSO, 353 K): δ
1
(203 mg, 0.20 mmol, 61%). H NMR (400 MHz, [D6]DMSO, 353
9.24 (d, J = 5.6 Hz, 2H, terpyridyl H), 8.66 (m, 5H, terpyridyl H), 8.52
(m, 2H, terpyridyl H), 7.95 (m, 2H, terpyridyl H), 7.66 (d, J = 8.0 Hz,
2H, phenyl H), 7.56 (d, J = 8.0 Hz, 2H, phenyl H), 4.69 (s, 2H,
−CH2N(CH3)2), 2.92 (s, 6H, −CH2N(CH3)2). IR (KBr disk, cm−1):
2123 [w, ν(CC)], 1186 [s, ν(SO)]. MS (FAB+): m/z 586.1 ([M
− OTf]+). Elem anal Calcd for C27H23F3N4O3PtS·CHCl3: C, 39.33; H,
2.83; N, 6.55. Found: C, 39.25; H, 3.08; N, 6.68.
K): δ 9.28 (d, J = 4.8 Hz, 2H, terpyridyl H), 9.07 (s, 2H, terpyridyl H),
8.88 (m, 2H, terpyridyl H), 8.57 (m, 2H, terpyridyl H), 8.34 (d, J = 8.0
Hz, 2H, phenyl H), 8.00 (m, 2H, terpyridyl H), 7.87 (d, J = 8.0 Hz,
2H, phenyl H), 7.57 (d, J = 8.0 Hz, 2H, phenyl H), 7.45 (d, J = 8.0 Hz,
2H, phenyl H), 4.69 (s, 2H, −CH2N+(CH3)3), 4.06 (s, 2H,
−CH2NH2), 3.13 (s, 9H, −CH2N+(CH3)3). IR (KBr disk, cm−1):
2118 [w, ν(CC)], 1169 [s, ν(SO)]. MS (FAB+): m/z 855.2 ([M
− OTf]+). Elem anal. Calcd for C36H33F6N5O6PtS2·CH2Cl2·
0.5CH3CN: C, 40.11; H, 3.28; N, 6.68. Found: C, 40.30; H, 3.30;
N, 6.68.
[Pt(tpy){CCC6H3(CH2NMe2)2-3,5}](OTf) (2). The procedure was
similar to that for complex 1 except that 1-ethynyl-3,5-bis(N,N-
dimethylamino)benzene (230 mg, 1.0 mmol) was used instead of 1-
ethynyl-4-(N,N-dimethylamino)benzene. The product was obtained as
1
[Pt{tpy(C6H4CH2NMe2-4)-4′}{CCC6H4(COOH)-4}](OTf) (7). The
procedure was similar to that for complex 3 except that [Pt{tpy-
(C6H4CH2NMe2-4)-4′}Cl](OTf) (224 mg, 0.33 mmol) was used
instead of [Pt{tpy(C6H4CH2NMe3-4)-4′}Cl](OTf)2. The product was
a dark-green solid (165 mg, 0.21 mmol, 63%). H NMR (400 MHz,
[D6]DMSO, 333 K): δ 9.24 (d, J = 5.2 Hz, 2H, terpyridyl H), 8.69 (m,
5H, terpyridyl H), 8.54 (m, 2H, terpyridyl H), 8.00 (m, 2H, terpyridyl
H), 7.38 (s, 2H, phenyl H), 7.23 (s, 1H, phenyl H), 3.53 (s, 4H,
−CH2N(CH3)2), 2.54 (s, 12H, −CH2N(CH3)2). IR (KBr disk, cm−1):
2117 [w, ν(CC)], 1168 [s, ν(SO)]. MS (FAB+): m/z 643.2 ([M
− OTf]+). Elem anal. Calcd for C30H30F3N5O3PtS·2CHCl3·CH3CN:
C, 38.07; H, 3.29; N, 7.84. Found: C, 38.26; H, 3.50; N, 7.60.
[Pt{tpy(C6H4CH2NMe3-4)-4′}{CCC6H4(COOH)-4}](OTf)2 (3). The
procedure was similar to that for complex 1 except that [Pt{tpy-
(C6H4CH2NMe3-4)-4′}Cl](OTf)2 (300 mg, 0.33 mmol) and 4-
ethynylbenzoic acid (146 mg, 1 mmol) were used instead of
[Pt(tpy)Cl](OTf) and 1-ethynyl-4-(N,N-dimethylamino)benzene, re-
spectively. The product was obtained as a red solid (150 mg, 0.15
mmol, 45%). 1H NMR (400 MHz, [D6]DMSO, 353 K): δ 9.29 (d, J =
5.3 Hz, 2H, terpyridyl H), 9.04 (s, 2H, terpyridyl H), 8.85 (d, J = 8.4
Hz, 2H, terpyridyl H), 8.59 (m, 2H, terpyridyl H), 8.32 (d, J = 8.4 Hz,
2H, phenyl H), 8.00 (m, 2H, terpyridyl H), 7.94 (d, J = 8.4 Hz, 2H,
phenyl H), 7.86 (d, J = 8.4 Hz, 2H, phenyl H), 7.61 (d, J = 8.4 Hz, 2H,
phenyl H), 4.68 (s, 2H, −CH2N+(CH3)3), 3.15 (s, 9H,
−CH2N+(CH3)3). IR (KBr disk, cm−1): 2118 [w, ν(CC)], 1696
[w, ν(CO)], 1172 [s, ν(SO)]. MS (FAB+): m/z 870 ([M −
OTf]+). Elem anal. Calcd for C36H30F6N4O8PtS2·H2O: C, 41.66; H,
3.11; N, 5.40. Found: C, 41.72; H, 3.13; N, 5.39.
[Pt{tpy(C6H4CH2NMe3-4)-4′}{CCC6H3(CH2NMe2)2-3,5}](OTf)2 (4).
The procedure was similar to that for complex 3 except that 1-ethynyl-
3,5-bis(N,N-dimethylamino)benzene (230 mg, 1.0 mmol) was used
instead of 4-ethynylbenzoic acid. The product was obtained as an
orange-red solid (211 mg, 0.2 mmol, 60%). 1H NMR (400 MHz,
[D6]DMSO, 353 K): δ 9.26 (d, J = 5.2 Hz, 2H, terpyridyl H), 9.06 (s,
2H, terpyridyl H), 8.87 (d, J = 8.0 Hz, 2H, terpyridyl H), 8.57 (m, 2H,
terpyridyl H), 8.33 (d, J = 8.0 Hz, 2H, phenyl H), 8.00 (m, 2H,
terpyridyl H), 7.87 (d, J = 8.0 Hz, 2H, phenyl H), 7.56 (s, 2H, phenyl
H), 7.37 (s, 1H, phenyl H), 4.69 (s, 2H, −CH2N+(CH3)3), 3.89 (s,
4H, −CH2N(CH3)2), 3.15 (s, 9H, −CH2N+(CH3)3), 2.53 (s, 12H,
−CH2N(CH3)2). IR (KBr disk, cm−1): 2117 [w, ν(CC)], 1184 [s,
ν(SO)]. MS (FAB+): m/z 940.2 ([M − OTf]+). Elem anal Calcd
for C41H44F6N6O6PtS2·2CHCl3: C, 38.87; H, 3.49; N, 6.32. Found: C,
38.54; H, 3.69; N, 6.04.
1
obtained as a brown solid (195 mg, 0.22 mmol, 67%). H NMR (400
MHz, [D6]DMSO, 353 K): δ 9.24 (d, J = 5.6 Hz, 2H, terpyridyl H),
9.01 (s, 2H, terpyridyl H), 8.85 (d, J = 8.0 Hz, 2H, terpyridyl H), 8.54
(m, 2H, terpyridyl H), 8.21 (d, J = 8.0 Hz, 2H, phenyl H), 7.97 (m,
2H, terpyridyl H), 7.93 (d, J = 8.0 Hz, 2H, phenyl H), 7.73 (d, J = 8.0
Hz, 2H, phenyl H), 7.60 (d, J = 8.0 Hz, 2H, phenyl H), 4.06 (s, 2H,
−CH2N(CH3)2), 2.58 (s, 6H, −CH2N(CH3)2). IR (KBr disk, cm−1):
2117 [w, ν(CC)], 1186 [s, ν(SO)]. MS (FAB+): m/z 706.1 ([M
− OTf]+). Elem anal. Calcd for C34H27F3N4O5PtS·1.5CHCl3·
0.5CH3CN: C, 41.54; H, 2.87; N, 5.97. Found: C, 41.69; H, 3.07;
N, 5.65.
[Pt{tpy(C6H4CH2NMe2-4)-4′}{CCC6H4−(COOCH3)-4}](OTf) (8).
The procedure was similar to that for complex 7 except that methyl
4-ethynylbenzoate (106 mg, 1.0 mmol) was used instead of 4-
ethynylbenzoic acid. The product was obtained as a dark-brown solid
1
(198 mg, 0.23 mmol, 69%). H NMR (300 MHz, CD3CN, 298 K): δ
8.46 (d, J = 5.2 Hz, 2H, terpyridyl H), 8.14 (m, 6H, terpyridyl H),
7.60−7.73 (m, 6H, phenyl and terpyridyl H), 7.40 (d, J = 6.0 Hz, 2H,
phenyl H), 7.14 (d, J = 6.0 Hz, 2H, phenyl H), 4.14 (s, 2H,
−CH2N(CH3)2), 3.89 (s, 3H, −COOCH3), 2.71 (s, 6H, −CH2N-
(CH3)2). IR (KBr disk, cm−1): 2118 [w, ν(CC)], 1195 [s, ν(S
O)]. MS (FAB+): m/z 720.2 ([M − OTf]+). Elem anal. Calcd for
C35H29F3N4O5PtS·1.5CHCl3: C, 41.80; H, 2.93; N, 5.34. Found: C,
41.60; H, 3.25; N, 5.36.
[Pt{tpy(C6H4CH2NMe2-4)-4′}(CCC6H5)](OTf) (9). The procedure
was similar to that for complex 7 except that 4-phenylacetylene (102
mg, 1.0 mmol) was used instead of 4-ethynylbenzoic acid. The product
1
was obtained as a purple-brown solid (155 mg, 0.19 mmol, 58%). H
NMR (400 MHz, [D6]DMSO, 353 K): δ 9.21 (d, J = 4.8 Hz, 2H,
terpyridyl H), 8.95 (s, 2H, terpyridyl H), 8.83 (d, J = 8.0 Hz, 2H,
terpyridyl H), 8.52 (m, 2H, terpyridyl H), 8.20 (d, J = 8.0 Hz, 2H,
phenyl H), 7.95 (m, 2H, terpyridyl H), 7.70 (d, J = 8.0 Hz, 2H, phenyl
H), 7.50 (d, J = 8.0 Hz, 2H, phenyl H), 7.34 (d, J = 8.0 Hz, 2H, phenyl
H), 7.27 (m, 1H, phenyl H), 4.01 (s, 2H, −CH2N(CH3)2), 2.56 (s,
6H, −CH2N(CH3)2). IR (KBr disk, cm−1): 2118 [w, ν(CC)], 1166
[s, ν(SO)]. MS (FAB+): m/z 662.2 ([M − OTf]+). Elem anal.
Calcd for C34H29F3N4O5PtS·2.5CHCl3·0.5CH3CN: C, 38.77; H, 2.76;
N, 5.57. Found: C, 38.85; H, 3.02; N, 5.59.
[Pt{tpy(C6H4CH2NMe3-4)-4′}{CCC6H4(CH2NMe2)-4}](OTf)2 (5).
The procedure was similar to that for complex 3 except that 1-
ethynyl-4-(N,N-dimethylamino)benzene (171 mg, 1.0 mmol) was
used instead of 4-ethynylbenzoic acid. The product was obtained as a
green solid (255 mg, 0.25 mmol, 75%). 1H NMR (400 MHz,
[D6]DMSO, 333 K): δ 9.27 (d, J = 6.8 Hz, 2H, terpyridyl H), 9.08 (s,
2H, terpyridyl H), 8.88 (d, J = 8.0 Hz, 2H, terpyridyl H), 8.58 (m, 2H,
terpyridyl H), 8.34 (d, J = 8.0 Hz, 2H, phenyl H), 7.99 (m, 2H,
terpyridyl H), 7.86 (d, J = 8.0 Hz, 2H, phenyl H), 7.60 (d, J = 8.0 Hz,
2H, phenyl H), 7.47 (d, J = 8.0 Hz, 2H, phenyl H), 4.67 (s, 2H,
−CH2N+(CH3)3), 4.18 (s, 2H, −CH2N(CH3)2), 3.15 (s, 9H,
−CH2N+(CH3)3), 2.70 (s, 6H, −CH2N(CH3)2). IR (KBr disk,
cm−1) 2119 [w, ν(CC)], 1169 [s, ν(SO)]. MS (FAB+): m/z
[Pt{tpy(C6H4CH2NMe2-4)-4′}{CCC6H4(CH2NMe3)-4}](OTf)2 (10).
The procedure was similar to that for complex 7 except that [HC
CC6H4CH2NMe3-4](OTf) (337 mg, 1.0 mmol) was used instead of 4-
ethynylbenzoic acid. The product was obtained as a dark-brown solid
1
(239 mg, 0.23 mmol, 70%). H NMR (400 MHz, CD3CN, 323 K): δ
9.19 (d, J = 4.8 Hz, 2H, terpyridyl H), 8.56 (s, 2H, terpyridyl H), 8.43
(m, 4H, terpyridyl H), 8.06 (d, J = 8.0 Hz, 2H, phenyl H), 7.89 (d, J =
8.0 Hz, 2H, phenyl H), 7.80 (m, 2H, terpyridyl H), 7.62 (d, J = 8.0 Hz,
2H, phenyl H), 7.47 (d, J = 8.0 Hz, 2H, phenyl H), 4.45 (s, 2H,
−CH2N+(CH3)3), 4.31 (s, 2H, −CH2N(CH3)2), 3.06 (s, 9H,
−CH2N+(CH3)3), 2.79 (s, 6H, −CH2N(CH3)2). IR (KBr disk,
K
Inorg. Chem. XXXX, XXX, XXX−XXX