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C(CH3)3); IR (KBr): ν=2109 cmÀ 1 (C�C); HRMS (ESI): m/z: [M+H]+
calculated for C52H45N2Pt: 892.3225; found: 892.3229; Elemental
analyses (%) for C52H44N2Pt: C, 70.02; H, 4.97; N, 3.14. Found: C,
70.16; H, 5.02; N, 3.17.
Complex 10: The synthesis was similar to that of complex 7. An
orange-red solid was obtained (65 mg, 72%). 1H NMR (400 MHz,
CD2Cl2): δ=9.37 (s, 2H; bpy), 8.64 (s, 2H; bpy and Ph), 7.84–7.90 (m,
4H; bpy), 7.61 (t, J=7.8 Hz, 4H; Ph), 7.54 (d, J=1.4 Hz, 2H; Ph), 7.38–
7.40 (m, 3H; Ph), 7.23–7.30 (m, 7H; Ph), 7.13 (d, J=8.3 Hz, 5H; Ph),
7.03 (t, J=7.3 Hz, 2H; Ph), 2.52 (s, 6H; CH3); IR (KBr): ν=2114 cmÀ 1
(C�C); HRMS (ESI): m/z: [M+H]+ calculated for C52H38N3Pt:
899.2708, found: 899.2675; Elemental analyses (%) for C52H37N3Pt: C,
69.48; H, 4.15; N, 4.67. Found: C, 69.29; H, 4.13; N, 4.53.
Complex 5: The synthesis was similar to that of complex 1. A yellow
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solid was obtained (52 mg, 74%). H NMR (400 MHz, DMSO-d6): δ=
9.40 (d, J=5.9 Hz, 2H; bpy), 9.11 (s, 2H; bpy), 8.84 (s, 1H; Ph), 8.21
(d, J=5.7 Hz, 2H; bpy), 8.04 (d, J=8.4 Hz, 4H; Ph), 7.65 (d, J=8.4 Hz,
4H; Ph), 7.58 (d, J=8.7 Hz, 4H; Ph), 7.38–7.28 (m, 6H; Ph), 1.36 (s,
18H; C(CH3)3); 19F NMR (376 MHz, DMSO-d6): δ=À 60.8. IR (KBr): ν=
2134 cmÀ 1 (C�C); HRMS (ESI): m/z: [M+H]+ C53H44N2F3Pt: 960.3099;
found: 960.3099; Elemental analyses (%) for C53H43F3N2Pt: C, 66.31;
H, 4.51; N, 2.92. Found: C, 66.28; H, 4.39; N, 2.88.
Complex 11: The synthesis was similar to modified that of complex
1. A red solid was obtained (30 mg, 50%). 1H NMR (500 MHz, DMSO-
d6): δ=9.76 (s, 2H; phen), 8.72 (s, 1H; Ph), 8.18 (d, J=5.0 Hz, 2H;
phen), 8.07 (s, 2H; phen), 7.92 (s, 2H; Ph), 7.85 (d, J=7.5 Hz, 2H; Ph),
7.69 (d, J=7.4 Hz, 2H; Ph), 7.63 (d, J=6.8 Hz, 4H; Ph), 7.57–7.51 (m,
1H; Ph), 7.35–7.24 (m, 8H; Ph); IR (KBr): ν=2136 cmÀ 1 (C�C); HRMS
(ESI): m/z: [MÀ 2Na]2À calculated for C46H26N2O6PtS2: 480.5445,
found:480.5454; Elemental analyses (%) for C46H26N2Na2O6PtS2: C,
54.82; H, 2.60; N, 2.78. Found: C, 54.61; H, 2.55; N, 2.75.
Complex 6: The synthesis was similar to that of complex 1. A yellow
1
solid was obtained (42 mg, 55%). H NMR (400 MHz, DMSO-d6): δ=
9.44 (d, J=5.9 Hz, 2H; bpy), 9.12 (s, 2H; bpy), 8.45 (s, 1H; Ph), 8.23
(d, J=5.9 Hz, 2H; bpy), 8.06 (d, J=8.5 Hz, 4H; Ph), 7.66 (d, J=8.5 Hz,
4H; Ph), 7.54 (d, J=7.6 Hz, 2H; Ph), 7.33 (t, J=7.9 Hz, 4H; Ph), 7.26 (t,
J=7.5 Hz, 2H; Ph), 7.21–7.11 (m, 8H; Ph), 7.06 (t, J=7.3 Hz, 2H; Ph),
6.89 (d, J=1.4 Hz, 2H; Ph), 1.37 (s, 18H; C(CH3)3); IR (KBr): ν=
2122 cmÀ 1 (C�C); HRMS (ESI): m/z: [M+H]+ calculated for
C64H54N3Pt: 1059.3960; found: 1059.3951; Elemental analyses (%) for
C64H53N3Pt: C, 72.57; H, 5.04; N, 3.97. Found: C, 72.22; H, 4.85; N,
4.01.
Complex 12: The synthesis was similar to that of complex 7. A red
solid was obtained (46 mg, 74%). 1H NMR (500 MHz, CDCl3): δ=9.55
(d, J=5.9 Hz, 2H; bipyrimidine), 8.44 (s, 1H; Ph), 8.17 (d, J=8.4 Hz,
4H; bipyrimidine and Ph), 7.79 (d, J=6.0 Hz, 2H; Ph), 7.59–7.54 (m,
2H; Ph), 7.53 (s, 2H; Ph), 7.52 (s, 2H; Ph), 7.42 (s, 1H; Ph), 7.25 (d, J=
1.7 Hz, 4H; Ph), 7.24–7.19 (m, 4H; Ph), 1.39 (s, 18H; C(CH3)3); 13C NMR
(126 MHz, CDCl3) δ=164.7 (bipyrimidine), 161.9 (bipyrimidine),
157.8 (bipyrimidine), 156.7 (bipyrimidine), 144.8 (Ph), 140.9 (Ph),
133.6 (Ph), 133.1 (Ph), 132.0 (Ph), 130.2 (Ph), 128.1 (Ph), 128.0 (Ph),
127.9 (Ph), 126.5 (Ph), 126.5 (Ph), 125.9 (Ph), 125.6 (Ph), 118.5 (Ph),
101.7 (PtÀ C�C), 85.5 (PtÀ C�C), 35.3 (C(CH3)3), 31.2 (C(CH3)3); IR
(KBr): ν=2110 cmÀ 1 (C�C); HRMS (ESI): m/z: [M+H]+ calculated for
C50H43N4Pt: 894.3130; found: 894.3118; Elemental analyses (%) for
C50H42N4Pt: C, 67.18; H, 4.74; N, 6.27. Found: C, 66.76; H, 4.76; N,
6.01.
Complex 7: A mixture of Pt(bpy)Cl2 (bpy=4,4’-bis(2,6-dimeth-
ylphenyl)-2,2’-bipyridine) (50 mg, 0.08 mmol), iPr2NH (1 mL, 722 mg,
7.14 mmol), L1 (40 mg, 0.12 mmol) and CuI (1 mg, 0.007 mmol) in
dry DCM (5 mL) was stirred at room temperature under dry N2 for
24 h. After removing dichloromethane under reduced pressure, the
residue purified by column chromatography on silica gel with
petroleum ether/dichloromethane (3:1) as eluent to afford a red
1
solid (40 mg, 56% yield). H NMR (500 MHz, CDCl3): δ=9.84 (d, J=
5.6 Hz, 2H; bpy), 8.65 (t, J=1.6 Hz, 1H; Ph), 7.76 (t, J=1.0 Hz, 2H;
bpy), 7.40 (m, 3H; bpy and Ph), 7.27 (dd, J=1.8, 1.7 Hz, 2H; Ph), 7.22
(t, J=7.6, 2H; Ph), 7.12 (s, 4H; Ph), 7.00 (d, J=11.35 Hz, 4H; Ph), 2.69
(s, 6H; CH3), 2.32 (s, 6H; CH3), 2.08 (s, 6H; CH3), 1.99 (s, 6H; CH3); 13C
NMR (126 MHz, CDCl3): δ=156.5 (bpy), 152.7 (bpy), 152.2 (bpy),
145.3 (bpy), 141.5 (bpy), 139.7 (Ph), 137.3 (Ph), 134.7 (Ph), 134.2
(Ph), 129.1 (Ph), 128.5 (Ph), 128.5 (Ph), 128.1 (Ph), 127.9 (Ph), 127.8
Complex 13: A mixture of Pt(bis-NHC)Cl2 (bis-NHC=bis(3-butyl-2,3-
dihydro-1H-imidazol-1-yl)methane) (50 mg, 0.09 mmol), iPr2NH
(1 mL, 722 mg, 7.14 mmol), L1 (50 mg, 0.18 mmol) and anhydrous
CuI (1 mg, 0.007 mmol) in dry DMF (5 mL) was stirred at room
temperature under dry N2 for 24 h. The solvent was removed under
reduced pressure. The residue was purified by column chromatog-
raphy with hexane/CH2Cl2 (5:1) to afford a pale-yellow solid (58 mg,
(Ph), 123.2 (Ph), 122.8 (Ph), 100.2 (PtÀ C�C), 89.4 (PtÀ C�C), 22.3
195
1
°
(CH3), 21.5 (CH3), 20.9 (CH3); Pt NMR (107 MHz, CDCl3, 25 C): δ=
83% yield). H NMR (500 MHz, CDCl3): δ=9.02 (s, 1H; Ph), 7.47 (d,
À 3583.4; IR (KBr): ν=2115 cmÀ 1 (C�C); HRMS (ESI): m/z: [M+H]+
calculated for C52H45N2Pt: 892.3225; found: 892.3230; Elemental
analyses (%) for C52H44N2Pt: C, 70.02; H, 4.97; N, 3.14. Found: C,
69.66; H, 4.81; N, 2.88.
J=7.2 Hz, 1H; Ph), 7.35 (d, J=6.6 Hz, 4H; Ph), 7.28 (s, 2H; Ph), 7.16
(s, 4H; Ph), 6.52 (d, J=13.6 Hz, 5H; carbene and À CHHÀ ), 5.07 (s, 2H;
CHHCH2CH2CH3), 4.49 (s, 1H; À CHHÀ ), 4.10 (s, 2H; CHHCH2CH2CH3),
1.70 (m, 4H; CH2CH2CH2CH3), 1.27 (m, 4H; CH2CH2CH2CH3), 0.86 (t,
J=6.9 Hz, 6H; CH2CH2CH2CH3); 13C NMR (126 MHz, CDCl3): δ=167.0
(C=Pt), 143.1 (Ph), 141.9 (Ph), 135.0 (Ph), 132.8 (Ph), 130.1 (Ph),
128.2 (Ph), 127.6 (Ph), 127.0 (Ph), 126.8 (Ph), 125.2 (Ph), 120.2
(carbene), 119.2 (carbene), 107.3 (PtÀ C�C), 106.8 (PtÀ C�C), 65.2
(À CH2À ), 50.3 (CH2CH2CH2CH3), 33.4 (CH2CH2CH2CH3), 19.9
Complex 8: The synthesis was similar to that of complex 7. An
orange solid was obtained (50 mg, 65%). 1H NMR (400 MHz, CD2Cl2):
δ=9.32 (s, 2H; bpy), 8.86 (s, 1H; Ph), 7.84 (s, 4H; bpy), 7.59 (d, J=
7.2 Hz, 2H; Ph), 7.33 (d, J=7.4 Hz, 2H; Ph), 7.18–7.27 (m, 6H; Ph),
6.96 (s, 2H; Ph), 2.50 (s, 6H; CH3), 2.31 (s, 3 H; CH3), 2.17 (s, 6H; CH3);
IR (KBr): ν=2130 cmÀ 1 (C�C); HRMS (ESI): m/z: [M+H]+ calculated
for C43H35N2Pt: 774.2443, found: 774.2430; Elemental analyses (%)
for C43H34N2Pt: C, 66.74; H, 4.43; N, 3.62. Found: C, 66.13; H, 4.16; N,
3.43.
(CH2CH2CH2CH3), 14.0 (CH2CH2CH2CH3); 195Pt NMR (107 MHz, CDCl3,
À 1
°
25 C): δ=À 4314.0; IR (KBr): ν=2112 cm (C�C); HRMS (ESI): m/z:
[M+H]+ calculated for C37H37N4Pt: 732.2661; found: 732.2672;
Elemental analyses (%) for C37H36N4Pt: C, 60.73; H, 4.96; N, 7.66.
Found: C, 60.58; H, 4.86; N, 7.52.
Complex 9: The synthesis was similar to that of complex 7. A yellow
solid was obtained (42 mg, 53%). 1H NMR (400 MHz, CD2Cl2): δ=
9.35 (s, 2H; bpy), 8.72 (s, 1H; Ph), 7.84–7.91 (m, 6H; bpy and Ph),
7.72 (d, J=8.1 Hz, 2H; Ph), 7.59–7.62 (m, 4H; Ph), 7.39 (d, J=7.4 Hz,
2H; Ph), 7.25–7.32 (m, 4H; Ph), 2.51 (s, 6 H; CH3); 19F NMR (376 MHz,
CD2Cl2): δ=À 62.6; IR (KBr): ν=2119 cmÀ 1 (C�C); HRMS (ESI): m/z:
[M+H]+ calculated for C41H28N2F3Pt: 800.1847, found: 800.1816;
Elemental analyses (%) for C41H27F3N2Pt: C, 61.57; H, 3.40; N, 3.50.
Found: C, 61.41; H, 3.35; N, 3.47.
Complex 14: The synthesis was similar to that of complex 13. A
pale-yellow solid was obtained (65 mg, 86% yield). 1H NMR
(400 MHz, CDCl3): δ=9.07 (s, 1H; Ph), 7.50 (s, 2H; Ph), 7.38 (dd, J=
6.1, 2.7 Hz, 2H; Ph), 7.26 (t, J=3.1 Hz, 2H; Ph), 7.22–7.14 (m, 4H; Ph),
6.68 (d, J=39.8 Hz, 4H; carbene), 5.91 (d, J=12.3 Hz, 1H; À CHHÀ ),
5.37 (s, 1H; -CHH-), 4.96 (s, 2H; CHHCH2CH2CH3), 4.26 (s, 2H;
CHHCH2CH2CH3), 1.79 (d, J=9.4 Hz, 4H; CH2CH2CH2CH3), 1.34 (s, 4H;
CH2CH2CH2CH3), 0.90 (t, J=7.3 Hz, 6H; CH2CH2CH2CH3); 13C NMR
(126 MHz, CDCl3): δ 167.1 (C=Pt), 142.3 (Ph), 142.2 (Ph), 137.8 (Ph),
Chem Asian J. 2021, 16, 1–16
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