Inorganic Chemistry
Article
1
in hexane). Yield: 72.3% (348 mg). H NMR (300 MHz, CD Cl ): δ
structure analysis: formula C H ClN PF Pt·C H O·2 × CH Cl , M
2
2
29 35
7
6
4
10
2
2
8
=
.56 (s, 2H), 8.12 (d, J = 7.9 Hz, 2H), 7.96−7.88 (m, 1H), 2.12 (dd, J
= 1101.12, yellow crystal, 0.40 × 0.07 × 0.07 mm, a = 17.3619(2), b =
13
3
53.0, 26.6 Hz, 18H), 1.79−1.60 (m, 12H). C NMR (75 MHz,
6.8895(1), c = 18.4882(3) Å, β = 102.457(1)°, V = 2159.40(5) Å , ρ
calc
−3
−1
CD Cl ): δ 151.38 (s), 147.64 (s), 138.63 (s), 119.47 (d, J = 61.7 Hz),
= 1.693 g cm , μ = 3.660 mm , empirical absorption correction
2
2
6
0.20 (s), 43.19 (s), 36.26 (s), 30.05 (s). HRMS (ESI) m/z:
(0.322 ≤ T ≤ 0.783), Z = 2, monoclinic, space group P2 /m (No. 11),
1
+
+
Calculated, 504.2851 [M + Na] ; found, 504.2845 [M + Na] . X-ray
crystal structure analysis: formula C H N , M = 481.64, yellow
crystal, 0.30 × 0.23 × 0.20 mm, a = 18.8888(4), b = 11.6902(2), c =
1
cm , μ = 0.080 mm , empirical absorption correction (0.976 ≤ T ≤
0
λ = 0.710 73 Å, T = 223(2) K, ω and φ scans, 13 947 reflections
−
1
collected (±h, ±k, ±l), [(sin θ)/λ] = 0.66 Å , 4082 independent (R
29
35
7
int
= 0.033) and 3977 observed reflections [I > 2σ(I)], 316 refined
parameters, R = 0.026, wR = 0.069, max (min) residual electron
density 1.34 (−0.78) e·Å , hydrogen atoms calculated and refined as
3
2
1.2906(2) Å, β = 96.767(1)°, V = 2475.75(8) Å , ρ = 1.292 g
calc
−3
−1
−3
.984), Z = 4, monoclinic, space group P2 /c (No. 14), λ = 0.710 73 Å,
riding atoms.
1
T = 223(2) K, ω and φ scans, 16 558 reflections collected (±h, ±k,
Synthesis of 2-Ph-Pt-Cl. 2-Ph (383 mg, 1.05 mmol) and
−1
±
l), [(sin θ)/λ] = 0.60 Å , 5779 independent (R = 0.048) and 4410
Pt(DMSO) Cl (422 mg, 1 mmol) were dissolved in dry MeOH
int
2
2
observed reflections [I > 2σ(I)], 353 refined parameters, R = 0.071,
and refluxed under N atmosphere for 48 h. After 1 h of reflux, a
2
2
−3
wR = 0.167, max (min) residual electron density 0.29 (−0.25) e·Å ,
yellow precipitate formed. After it cooled to rt, the yellow precipitate
hydrogen atoms calculated and refined as riding atoms.
was filtered and washed with Et O to remove traces of unreacted 2-Ph.
2
Synthesis of Phenylazide. Phenylazide was synthesized by
following a literature report. Aniline (1.567 mL, 17.2 mmol) was
Then the crude product was redissolved in a minimum amount of
72
DMSO by gentle heating. An aqueous solution of NH PF was added
4
6
dissolved in ACN and cooled to 0 °C. To this mixture, t-BuNO (3
(dropwise), and a precipitate formed, which was filtered off and
2
mL, 25.6 mmol) was added followed by dropwise addition of
trimethylsilyl azide (2.72 mL, 20.4 mmol). The reaction mixture was
left stirring at rt for 2.5 h. The reaction mixture was concentrated
under reduced pressure, and the product was purified by column
washed with water to remove the excess of NH PF . The crude was
4
6
purified by column chromatography (neutral Al
in DCM). Yield: 80% (505 mg). H NMR (300 MHz, DMSO-d ): δ
O
, 10−15% MeOH
2
3
1
6
9.38 (s, 2H), 8.11−8.05 (m, 2H), 8.05−7.98 (m, 1H), 7.71−7.61 (m,
13
chromatography (silica gel, hexane). The product constituted a yellow
4H), 7.59−7.50 (m, 4H), 7.45−7.34 (m, 2H). C NMR (75 MHz,
1
oil. Yield: 75% (1530 mg). H NMR (300 MHz, CDCl ): δ 7.41−7.33
DMSO-d
): δ 149.46 (s), 148.18 (s), 138.68 (s), 136.58 (s), 130.04
6
3
(
m, 1H), 7.19−7.11 (m, 1H), 7.04 (ddd, J = 2.8, 2.3, 1.1 Hz, 1H).
Synthesis of 2,6-Bis(3-phenyl-1H-1,2,3-triazol-5-yl)pyridine
2-Ph). In a 100 mL round-bottom flask, compound 1 (204 mg, 1.6
(s), 129.10 (s), 121.94 (s), 120.39 (s), 118.86 (s). HRMS (ESI) m/z:
+
+
Calculated, 596.0711 [M] ; found, 596.0688 [M] , 591.1203 [M − Cl
+
(
+ OCH ] . CHN Analysis: Calculated (C H ClN PF Pt), C,
3
21 15
7
6
mmol) and phenylazide (400 mg, 3.36 mmol) were dissolved in a
39.95%; H, 2.39%; N, 15.53%; found, C, 39.67%; H, 2.54%; N,
15.19%. X-ray crystal structure analysis: formula C H ClN PF Pt, M
mixture of t-BuOH/water (1:1) (16 mL) under N . Sodium ascorbate
2
21 15
7
6
(
158 mg, 0.8 mmol) and CuSO ·5H O (80 mg, 0.32 mmol) were
= 740.91, yellow crystal, 0.12 × 0.06 × 0.02 mm, a = 6.8613(2), b =
4
2
added, and the reaction mixture was stirred at rt under N for 24 h. To
17.8733(4), c = 20.9936(4) Å, α = 72.697(1), β = 87.112(1), γ =
2
3
−3
−1
get rid of the copper salts, an aqueous ammonia solution was added to
reaction mixture and stirred for 1 h. The product was then extracted
into DCM. The organic layer was washed with brine and dried over
83.748(1)°, V = 2442.9(1) Å , ρ = 2.014 g cm , μ = 5.990 mm ,
calc
empirical absorption correction (0.533 ≤ T ≤ 0.889), Z = 4, triclinic,
̅
space group P1 (No. 2), λ = 0.710 73 Å, T = 223(2) K, ω and φ scans,
−1
MgSO followed by removal of the solvent using a rotary evaporator.
20 859 reflections collected (±h, ±k, ±l), [(sin θ)/λ] = 0.59 Å , 8390
independent (Rint = 0.039) and 7478 observed reflections [I > 2σ(I)],
4
The crude mixture was purified by column chromatography (silica gel,
1
2
5
0% EtOAc in hexane). Yield: 80% (467 mg). H NMR (300 MHz,
667 refined parameters, R = 0.069, wR = 0.192, max (min) residual
−3
CDCl ): δ 8.73 (s, 2H), 8.26−8.17 (m, 2H), 7.99−7.90 (m, 1H),
electron density 1.88 (−1.88) e·Å , hydrogen atoms calculated and
3
13
7
.87−7.77 (m, 4H), 7.59−7.50 (m, 4H), 7.50−7.41 (m, 2H).
NMR (75 MHz, CDCl ): δ 149.77 (s), 148.70 (s), 138.25 (s), 137.06
C
refined as riding atoms.
3
Synthesis of 2-Ad-Pt-CN. A mixture of 2-Ad-Pt-Cl (85.7 mg, 0.1
mmol) and AgCN (24 mg, 0.18 mmol) in ACN was heated at 65 °C
(
(
s), 129.93 (s), 129.07 (s), 120.54 (d, J = 13.0 Hz), 119.98 (s). HRMS
+
ESI) m/z: Calculated, 388.1286 [M + Na] ; found, 388.1281 [M +
for 4 h under N atmosphere. The hot reaction mixture was filtered
2
+
+
Na] , 366.1452 [M + H] .
through a pad of Celite. The filtrate was concentrated under vacuum
and further purified by column chromatography (silica gel, 5% MeOH
Synthesis of Pt(DMSO) Cl . K PtCl (5 g, 1 equiv) and DMSO
2.6 mL, 3 equiv) were dissolved in 50 mL of water in a one necked
2
2
2
4
1
(
in DCM). Yield: 65% (55.1 mg). H NMR (300 MHz, CD Cl ): δ
2
2
round-bottom flask. This reaction mixture was stirred at rt for 4 h.
During this period, an ash-colored precipitate was formed, which was
8.66 (s, 2H), 8.23 (dd, J = 8.5, 7.6 Hz, 1H), 8.02 (d, J = 7.9 Hz, 2H),
2.36 (s, 18H), 1.84 (s, 12H). 13C NMR (75 MHz, CD Cl ): δ 151.13
2
2
removed by filtration, washed with water, and then washed with Et O.
The product was dried under vacuum before further usage. Yield:
(s), 148.70 (s), 144.62 (s), 124.92 (s), 121.34 (s), 66.29 (s), 42.79 (s),
2
35.81 (s), 30.21 (s). 19F NMR (282 MHz, CD Cl ): δ −70.40 (d, J =
2
2
8
4.2% (4.283 g).
1.0 Hz), −72.92 (d, J = 1.0 Hz). HRMS (ESI) m/z: Calculated,
+
+
Synthesis of 2-Ad-Pt-Cl. 2-Ad (505 mg, 1.05 mmol) and
702.2629 [M] ; found, 702.2621 [M] . CHN Analysis: Calculated
(C H N PF Pt+MeOH), C, 42.32%; H, 4.47%; N, 12.74%; found,
Pt(DMSO) Cl (422 mg, 1 mmol) were dissolved in dry MeOH
2
2
30 35
8
6
and refluxed under N for 48 h. After 1 h of reflux, a yellow precipitate
C, 42.19%; H, 4.47%; N, 12.45%. X-ray crystal structure analysis:
2
formed. After it cooled to rt, the yellow precipitate was filtered and
formula C H N PF Pt·3 × C H N, M = 970.88, yellow crystal, 0.50
30
35
8
6
2
3
washed with Et O to remove traces of unreacted 2-Ad. Then the crude
× 0.07 × 0.01 mm, a = 19.6031(4), b = 13.6843(3), c = 29.6267(6) Å,
2
3
−3
product was redissolved in a minimum amount of DMSO by gentle
heating. An aqueous solution of NH PF was added (dropwise), and a
β = 95.421(1)°, V = 7912.0(3) Å , ρ = 1.630 g cm , μ = 3.658
calc
1
−
mm , empirical absorption correction (0.262 ≤ T ≤ 0.964), Z = 8,
monoclinic, space group P2 /n (No. 14), λ = 0.710 73 Å, T = 223(2)
4
6
precipitate formed, which was filtered off and washed with water to
1
remove the excess of NH PF . The precipitate was further washed with
K, ω and φ scans, 54 298 reflections collected (±h, ±k, ±l), [(sin θ)/
4
6
−1
Et O, and the crude product was purified by column chromatography
λ] = 0.59 Å , 13 670 independent (R = 0.088) and 11 062 observed
2
int
1
2
(
(
(
silica gel, 5−10% MeOH in DCM). Yield: 75% (642 mg). H NMR
300 MHz, DMSO-d ): δ 9.48 (s, 2H), 8.40 (t, J = 8.0 Hz, 1H), 7.98
d, J = 8.0 Hz, 2H), 2.23 (s, 18H), 1.72 (s, 12H). C NMR (75 MHz,
reflections [I > 2σ(I)], 997 refined parameters, R = 0.066, wR = 0.142,
max (min) residual electron density 1.28 (−1.30) e·Å , hydrogen
−3
6
13
atoms calculated and refined as riding atoms.
DMSO-d ): δ 150.17 (s), 147.76 (s), 143.32 (s), 125.66 (s), 120.37
Synthesis of 2-Ph-Pt-CN. A mixture of 2-Ph-Pt-Cl (74 mg, 0.1
mmol) and AgCN (24 mg, 0.18 mmol) in ACN was heated at 65 °C
6
19
(
s), 64.16 (s), 41.64 (s), 34.93 (s), 29.00 (s). F NMR (282 MHz,
DMSO-d ): δ −68.87 (s), −71.39 (s). HRMS (ESI) m/z: Calculated,
7
CHN Analysis: Calculated (C H ClN PF Pt), C, 40.64%; H, 4.12%;
for 4 h under N atmosphere. The hot reaction mixture was filtered
6
2
+
+
+
12.2283 [M] ; found, 712.2280 [M] , 707.2790 [M − Cl + OCH ] .
through a pad of Celite to remove the precipitated silver chloride. The
filtrate was concentrated under vacuum and further purified by column
chromatography (neutral Al O , 5−10% MeOH in DCM). Yield: 62%
3
29
35
7
6
N, 11.44%; found, C, 40.80%; H, 4.16%; N, 11.14%. X-ray crystal
2
3
G
Inorg. Chem. XXXX, XXX, XXX−XXX