Inorganic Chemistry
Article
7.20 (s, 1H), 7.16 (dd, J = 8.4, 5.3 Hz, 1H), 3.66 (s, 6H), 2.55 (s,
3H), 2.50 (s, 3H). 13C NMR (75 MHz, CDCl3): δ 162.0, 146.9,
143.6, 135.9, 133.2, 127.9, 125.3, 120.5, 119.0, 46.3, 16.9, 15.9. 195Pt
NMR (64.5 MHz, CDCl3): δ −2776.5. HRMS (ESI) calculated for
C13H16ClNO2PtS, [M]+: 480.0289. Found: 480.0280.
Hz, 2JP,P = 24.3 Hz), −1.3 (1JPt,P = 3716.6 Hz, 2JP−P = 24.3 Hz). 195Pt
1
NMR (64.5 MHz, CDCl3): δ −4154.0 (dd, JPt,P = 3709.4, 3560.7
Hz). HRMS (ESI+) calculated for C45H34NO2P2Pt+, [M]+: 877.1711,
Found: 877.1684.
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Complex [Pt9]Cl. Yellow solid (193.5 mg, 97% yield). H NMR
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Complex Pt3. Red solid (161.9 mg, 80% yield). H NMR (300
(300 MHz, CDCl3): δ 8.55−8.15 (m, 2H), 7.93−7.71 (m, 3H),
7.70−7.52 (m, 8H), 7.51−7.29 (m, 10H), 7.27−7.07 (m, 6H), 7.04
(d, J = 7.9 Hz, 1H), 7.00−6.89 (m, 3H), 6.85−6.69 (m, 4H), 6.64 (d,
J = 7.9 Hz, 1H). 13C NMR (75 MHz, CDCl3): δ 148.5, 141.1, 137.2,
135.6, 135.5, 135.4, 135.3, 134.4 (2C), 134.3 (2C), 133.9, 133.4,
133.3, 133.2 (2C), 131.9 (2C), 131.4 (2C), 131.3, 131.2, 130.3,
130.2, 130.1, 130.0, 128.8, 128.6, 128.4, 128.3 (2C), 128.2, 127.9,
127.8, 127.7 (2C), 127.6, 127.5, 127.4 (2C), 127.2 (3C), 127.1, 125.5
(2C), 123.9 (2C), 121.2 (2C) 121.0 (2C), 120.4, 116.3, 114.5 (all the
C signals are listed). 31P NMR (122 MHz, CDCl3): δ 6.5 (2JP,P = 29.9
Hz), 5.1 (2JP,P = 29.9 Hz). 195Pt NMR (64.5 MHz, CDCl3): δ
MHz, CDCl3): δ 9.34 (dd, J = 5.4, 1.3 Hz, 1H), 8.62 (dd, J = 8.4, 1.3
Hz, 1H), 7.28 (dd, J = 8.4, 5.4 Hz, 1H), 7.12 (d, J = 8.6 Hz, 1H), 6.91
(d, J = 8.6 Hz, 1H), 3.95 (s, 3H), 3.65 (s, 6H). 13C NMR (75 MHz,
CDCl3): δ 160.1, 148.1, 145.6, 144.0, 134.9, 122.3, 119.8, 113.9,
108.6, 56.6, 46.3. 195Pt NMR (64.5 MHz, CDCl3): δ −2764.1. HRMS
(ESI) calculated for C12H14ClNO3PtSNa+, [M+Na+]+: 504.9924.
Found: 504.9928.
Complex Pt4.6,9 Red solid (185.6 mg, 95% yield). H NMR (300
1
MHz, CDCl3): δ 9.36 (d, J = 4.0 Hz, 1H), 8.66 (d, J = 8.7 Hz, 1H),
7.76−7.72 (m, 1H), 7.63 (t, J = 7.8 Hz, 1H), 7.55−7.48 (m, 2H),
3.61 (s, 6H).
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−4035.2 (dd, JPt,P = 3568.1, 3418.9 Hz). HRMS (ESI+) calculated
General Procedure for the Synthesis of Complexes [Pt5]Cl−
[Pt13]Cl. In a Schlenk flask, the corresponding complex Pt1−Pt4
(0.2 mmol, 1.0 equiv) and phosphine ligand (0.2 mmol for bidentate
phosphines or 0.4 mmol for monodentate phosphines) were added.
Then, 2.0 mL of chloroform were added under nitrogen, and the
reaction mixture was refluxed for 24 h. Next, the solvent was removed
under reduced pressure, and the resultant solid was washed with cold
diethyl ether and dried under a vacuum.
for C53H38NOP2Pt+, [M]+: 961.2076. Found: 961.2057.
Complex [Pt10]Cl. Brown solid (195.1 mg, 99% yield). H NMR
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(300 MHz, CDCl3): δ 8.28 (d, J = 7.7 Hz, 1H), 8.20−8.05 (m, 1H),
7.91−7.66 (m, 3H), 7.60−7.45 (m, 8H), 7.44−7.33 (m, 8H), 7.30−
7.24 (m, 2H), 7.00 (d, J = 8.0 Hz, 1H), 6.91 (dd, J = 8.1, 5.3 Hz, 1H),
6.59 (d, J = 7.8 Hz, 1H), 6.53 (dd, J = 12.8, 8.3 Hz, 1H), 6.40 (dd, J =
8.1, 1.4 Hz, 1H), 6.36−6.24 (m, 2H), 5.91 (d, J = 6.5 Hz, 2H), 5.87
(s, 1H), 5.66 (s, 1H). 13C NMR (75 MHz, CDCl3): δ 166.6 (2C),
166.5 (2C), 151.1 (3C), 151.0, 148.5, 147.5, 147.3, 147.1, 147.0,
144.0, 141.0, 134.9, 134.8, 133.2 (2C), 133.0, 132.9, 132.7 (2C),
132.1 (2C), 131.2, 131.1, 130.1 (3C), 130.0, 129.5, 129.3, 129.1,
129.0, 128.9, 128.7, 128.6, 128.2, 128.0, 120.9, 118.5, 116.3, 116.2,
114.4, 109.0, 108.9, 108.8, 108.6, 102.7, 102.6 (all the C signals are
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Complex [Pt5]Cl. Brown solid (158.3 mg, 88% yield). H NMR
(300 MHz, CDCl3): δ 8.38 (d, J = 8.2 Hz, 1H), 7.63−7.32 (m, 21H),
7.32−7.26 (m, 4H), 7.24−7.15 (m, 7H), 7.08−6.97 (m, 2H), 6.46 (d,
J = 7.8 Hz, 1H). 13C NMR (75 MHz, CDCl3): δ 149.1, 141.7, 135.2,
135.1 (2C), 135.0, 134.9 (2C), 134.7, 134.6, 134.4, 134.3, 132.8
(2C), 132.5, 132.3 (3C), 131.1 (3C), 130.9, 129.4, 129.2, 128.9,
128.7, 128.6, 128.4, 128.2, 128.1, 128.0, 127.9, 126.6, 125.7, 121.1,
listed). 31P NMR (122 MHz, CDCl3): δ 4.0 (1JPt,P = 3561.1 Hz, 2JP,P
=
2
30.4 Hz), 3.5 (1JPt,P = 3435.1 Hz, JP,P = 30.1 Hz). 195Pt NMR (64.5
114.9, 113.2 (all the C signals are listed). 31P NMR (122 MHz,
1
MHz, CDCl3): δ −4089.2 (dd, JPt,P = 3582.9, 3393.6 Hz). HRMS
2
CDCl3): δ 14.1 (1JPt,P = 3672.5 Hz, JP,P = 25.0 Hz), 8.7 (1JPt,P
=
(ESI+) calculated for C47H34NO5P2Pt+, [M]+: 949.1559. Found:
949.1557.
3394.3 Hz, JP,P = 25.0 Hz). 195Pt NMR (64.5 MHz, CDCl3): δ
4210.3 (dd, 1JPt,P = 3675.2, 3398.3 Hz). HRMS (ESI+) calculated for
C45H36NOP2Pt+, [M]+: 863.1919. Found: 863.1916.
2
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Complex [Pt11]Cl. Red solid (184.5 mg, 98% yield). H NMR
(300 MHz, CDCl3): δ 8.39 (d, J = 8.3 Hz, 1H), 8.31−7.73 (m, 5H),
7.67 (t, J = 7.7 Hz, 1H), 7.62−7.33 (m, 8H), 7.34−7.08 (m, 12H),
6.98−6.84 (m, 2H), 6.64−6.48 (m, 2H), 6.05 (ddd, J = 11.3, 7.7, 1.4
Hz, 1H), 2.58 (s, 6H). 13C NMR (75 MHz, CDCl3): δ 161.9, 159.2
(2C), 159.0, 158.9, 149.0 (2C), 144.7, 144.6 (2C), 138.3, 138.0 (2C),
135.3, 135.1, 134.7 (2C), 134.5 (2C), 133.9, 132.8, 129.6, 128.6
(2C), 126.9, 126.3, 126.2, 125.3 (2C), 125.2, 125.0, 121.7, 120.2,
119.4, 119.3 (2C), 119.1, 16.9 (2C; all the C signals are listed). 31P
NMR (122 MHz, CDCl3): δ 3.1 (1JPt,P = 3531.1 Hz, 2JP,P = 24.8 Hz),
1
Complex [Pt6]Cl. Brown solid (213.7 mg, 99% yield). H NMR
(300 MHz, CDCl3): δ 8.28 (d, J = 7.6 Hz, 1H), 7.60 (t, J = 4.9 Hz,
1H), 7.40−7−19 (m, 13H), 7.01−6.92 (m, 2H), 6.71 (dd, J = 8.8, 2.0
Hz, 6H), 6.63 (dd, J = 8.8, 2.0 Hz, 6H), 6.47 (d, J = 7.2 Hz, 1H), 3.74
(s, 9H), 3.72 (s, 9H). 13C NMR (75 MHz, CDCl3): δ 165.4, 161.5,
161.4, 161.3 (2C), 148.0, 143.9, 140.2, 135.6, 135.5, 135.0, 134.8,
130.2, 129.9, 119.9, 118.3, 117.4, 117.2, 116.2, 115.2, 113.6, 113.4,
113.3, 113.1, 112.9, 54.7 (2C) (all the C signals are listed). 31P NMR
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(122 MHz, CDCl3): δ 10.7 (1JPt,P = 3693.9 Hz, JP,P = 24.6 Hz), 4.9
2
−1.3 (1JPt,P = 3688.5 Hz, JP,P = 24.8 Hz). 195Pt NMR (64.5 MHz,
(1JPt,P = 3423.0 Hz, 2JP,P = 24.6 Hz). 195Pt NMR (64.5 MHz, CDCl3):
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CDCl3): δ −4149.2 (dd, JPt,P = 3678.1, 3552.0 Hz). HRMS (ESI+)
1
δ 4211.0 (dd, JPt,P = 3684.6, 3426.2 Hz). HRMS (ESI+) calculated
calculated for C47H38ClNO2P2Pt+, [M]+: 905.2024. Found: 905.2034.
for C51H48NO7P2Pt+, [M]+: 1043.2553. Found: 1043.2566.
Complex [Pt7]Cl. Brown solid (142.6 mg, 89% yield). H NMR
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Complex [Pt12]Cl. Dark yellow solid (171.7 mg, 91% yield). H
1
NMR (300 MHz, CDCl3): δ 8.65 (d, J = 7.7 H, 1H), 8.35−7.76 (m,
4H), 7.70 (t, J = 7.7 Hz, 1H), 7.65−7.27 (m, 12H), 7.25−7.01 (m,
9H), 6.93 (dd, J = 7.2, 5.6 Hz, 1H), 6.83 (d, J = 8.6 Hz, 1H), 6.65−
6.51 (m, 2H), 6.48 (d, J = 8.5 Hz, 1H), 6.10 (dd, J = 10.2, 7.7 Hz,
1H), 3.88 (s, 3H). 13C NMR (75 MHz, CDCl3): δ 159.4, 159.3, 159.0
(2C), 158.8 (2C), 149.7 (2C), 145.8, 144.6, 144.5 (2C), 137.8, 136.8,
135.1, 135.0, 134.8, 134.7, 134.4 (2C), 133.7, 132.7 (2C), 131.8,
129.4, 126.3, 126.2, 125.3, 125.2, 125.0, 124.9, 122.8 (2C), 121.1
(2C), 120.2, 120.1, 119.8, 119.6, 119.5 (2C), 119.2, 119.1, 118.8,
114.4, 114.3, 108.8, 56.6 (all the C signals are listed). 31P NMR (122
MHz, CDCl3): δ 2.6 (1JPt,P = 3521.0 Hz, 2JP,P = 24.4 Hz), −1.2 (1JPt,P
(300 MHz, CDCl3): δ 8.29 (d, J = 8.1 Hz, 1H), 7.84 (dd, J = 11.3, 7.8
Hz, 4H), 7.67 (dd, J = 11.6, 7.9 Hz, 4H), 7.58−7.33 (m, 14H), 6.98
(d, J = 7.8 Hz, 2H), 6.62 (d, J = 7.8 Hz, 1H), 3.01−2.71 (m, 2H),
2.43 (s, 2H), 2.21−1.85 (m, 4H). 13C NMR (75 MHz, CDCl3): δ
166.5, 148.2, 144.4, 141.0, 133.9, 133.8, 133.6, 133.5, 133.4, 132.8,
132.1, 131.2, 131.1, 131.0, 129.9, 129.8, 128.9, 128.7, 128.4, 128.3
(2C), 128.1, 127.7, 127.6, 127.2, 126.8, 120.7, 116.3, 114.3, 28.2, 27.7,
26.2, 25.7, 23.3, 22.5 (all the C signals are listed). 31P NMR (122
MHz, CDCl3): δ 9.5 (1JPt,P = 3432.9 Hz, 2JP,P = 29.0 Hz), 4.2 (1JPt,P
=
2
3315.7 Hz, JP,P = 29.0 Hz). 195Pt NMR (64.5 MHz, CDCl3): δ
1
−4264.4 (t, JPt,P = 3392.1 Hz). HRMS (ESI+) calculated for
2
= 3733.0 Hz, JP,P = 24.4 Hz). 195Pt NMR (64.5 MHz, CDCl3): δ
C37H34NOP2Pt+, [M]+: 765.1762. Found: 765.1760.
Complex [Pt8]Cl. Yellow solid (173.5 mg, 95% yield). H NMR
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−4136.4 (dd, JPt,P = 3733.2, 3521.3 Hz). HRMS (ESI+) calculated
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for C46H36NO3P2Pt+, [M]+: 907.1817. Found: 907.1829.
Complex [Pt13]Cl. Orange solid (153.1 mg, 97% yield). 1H NMR
(300 MHz, CDCl3): δ 8.73−8.62 (m, 1H), 6.61−8.55 (m, 1H),
7.92−7.80 (m, 8H), 7.58−7.48 (m, 12H), 7.25−7.18 (m, 4H), 3.05−
2.65 (m, 4H). 13C NMR (75 MHz, CDCl3): δ 155.0, 154.9, 150.0,
144.1, 142.8, 134.1, 134.0, 133.7, 133.5, 133.1 (2C), 132.8 (2C),
132.0, 131.6, 130.2, 130.0, 129.5, 129.3, 126.6, 126.3, 125.8, 125.6,
123.4, 122.2, 29.8, 29.7, 29.6, 29.5, 29.2 (2C), 29.0, 28.9 (all the C
(300 MHz, CDCl3): δ 8.39 (d, J = 8.1 Hz, 1H), 8.14 (s, 2H), 7.86−
6.97 (m, 27H), 6.60 (dd, J = 16.4, 8.1 Hz, 3H), 6.19−6.02 (m, 1H).
13C NMR (75 MHz, CDCl3): δ 166.0, 159.1, 159.0, 158.9, 158.8,
149.3 (2C), 141.7, 137.9 (2C), 135.2, 135.0, 134.8, 134.5, 132.8
(2C), 131.9, 131.2, 131.1, 129.6, 126.4, 126.3, 125.4, 125.3, 125.1,
125.0, 121.1, 121.0, 120.9, 119.2, 119.1, 116.2, 116.1, 114.7 (all the C
signals are listed). 31P NMR (122 MHz, CDCl3): δ 2.5 (1JPt,P = 3553.1
I
Inorg. Chem. XXXX, XXX, XXX−XXX