Dalton Transactions
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CDCl3, δ)/COSY: 7.54–7.43 (m, 30H, Ar–H), 5.53 (d, JHH = 12.4 (C–O), 169.36 (C–O), 135.12 (Cquat–Ph), 129.78 (HC–Ph), 129.6
Hz, 3H, NCH2N), 5.21 (d, J = 14.4 Hz, 3H, PCH2N), 4.94 (d, (HC–Ph), 128.4 (HC–Ph), 128.18 (HC–Ph), 127.82 (HC–Ph),
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2JHH = 11.2 Hz, 3H, NCH2N), 4.61 (d, JHH = 10.4 Hz, 3H, 127.28 (HC–Ph), 68.14 (NCH2N), 61.71 (NCH2N), 46.48
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NCH2N), 4.34 (d, J = 14.8 Hz, 3H, PCH2N), 4.12 (d, JHH = 11.2 (PCH2N), 45.26 (PCH2N), 38.24 (PCH2N). DEPT (400 MHz,
Hz, 3H, NCH2N), 3.78 (m, 3H, PCH2N), 3.54 (br s, 9H, PCH2N). DMSO-d6, δ): 129.52, 129.34, 128.15, 127.93, 127.57, 127.02,
31P{1H} NMR (400 MHz, CDCl3, δ): −78.61 (br s). 13C{1H} NMR 67.88, 61.44, 46.25, 44.99, 37.98. ESI(+)MS in MeOH (m/z
(400 MHz, CDCl3, δ)/DEPT/HSQC: 171.44 (C–O), 171.08 (C–O), assignment,
%
intensity): 769 ([Cu{DBPTA}2]+, 12), 414
135.02 (Cquat–Ph), 134.79 (Cquat–Ph), 130.32 (HC–Ph), 130.05 ([Cu{DBPTA}]+, 100), 354 ([{DBPTA} + H]+, 25).
(HC–Ph), 128.94 (HC–Ph), 128.65 (HC–Ph), 128.03 (HC–Ph),
4.4. Synthesis of [Cu(μ-Br)(DBPTA)2]2 (5)
127.48 (HC–Ph), 69.01 (NCH2N), 62.67 (NCH2N), 47.04
(PCH2N), 45.25 (PCH2N), 38.13 (PCH2N). DEPT (400 MHz, To an acetonitrile solution (5 mL) of CuBr (20 mg, 0.14 mmol,
CDCl3, δ): 130.01, 129.84, 128.74, 128.45, 127.82, 127.26, 68.81, 1 equiv.) was added an acetonitrile solution (5 mL) of 1
62.47, 46.83, 45.02, 37.89. 1H NMR (300 MHz, DMSO-d6, (100 mg, 0.28 mmol, 2 equiv.) dropwise with stirring for
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δ)/COSY: 7.43 (br s, 30H, Ar–H), 5.25 (d, JHH = 13.2 Hz, 3H, 30 min at room temperature. The produced colourless solution
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NCH2N), 4.98 (d, J = 15.3 Hz, 3H, PCH2N), 4.77 (d, JHH = 12 was stirred at room temperature overnight, and then the reac-
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Hz, 3H, NCH2N), 4.65 (d, JHH = 12.6 Hz, 3H, NCH2N), tion mixture was reduced under vacuum to ca. 2 mL. 5 mL of
4.23–4.09 (m, 3H NCH2N, 3H PCH2N), 3.94 (dd, 2JHP = 13.2 Hz, petroleum ether were added to produce compound 5 as a
2JHH = 7.8 Hz, 3H, PCH2N), 3.59 (br s, 9H, PCH2N). 31P{1H} white solid, which was then filtered off, repeatedly washed
NMR (400 MHz, DMSO-d6, δ): −63.22 (br s). 13C{1H} NMR with petroleum ether and dried under vacuum.
(300 MHz, DMSO-d6, δ)/DEPT/HSQC: 169.76 (C–O), 169.37
Yield = 73.9% (88 mg) based on the metal salt. Elemental
(C–O), 135.34 (Cquat–Ph), 129.68 (HC–Ph), 129.49 (HC–Ph), analysis calcd (%) for C76H80Br2Cu2N12O8P4: C 53.68, H 4.74,
128.41 (HC–Ph), 128.16 (HC–Ph), 127.79 (HC–Ph), 127.22 (HC– N 9.89; found: C 53.36, H 5.01, N 9.59. FTIR (KBr): ν (cm−1) =
Ph), 68.12 (NCH2N), 61.74 (NCH2N), 45.64 (PCH2N), 44.48 2281 w, 2116 w, 1905 w, 1614 s, 1575 m, 1490 w, 1404 m,
(PCH2N), 37.59 (PCH2N). DEPT (300 MHz, DMSO-d6, δ): 1336 m, 1238 m, 1126 w, 1075 m, 1001 m, 921 w, 889 w, 858 w,
129.43, 129.25, 128.16, 127.9, 127.54, 126.97, 67.94, 61.48, 787 m, 698 s, 651 m, 509 m. 1H NMR (400 MHz, CDCl3, δ):
45.38, 44.24, 37.32. ESI(+)MS in MeOH (m/z assignment, 7.53–7.43 (m, 40H, Ar–H), 5.47 (d, 2JHH = 11.2 Hz, 4H, NCH2N),
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% intensity): 1474 ([Cu{DBPTA}4]+, 13), 1153 ([Cu{DBPTA}3
+
5.16 (d, J = 15.6 Hz, 4H, PCH2N), 4.88 (d, JHH = 8 Hz, 4H,
MeOH]+, 19), 801 ([Cu{DBPTA}2
+
MeOH]+, 22), 769 NCH2N), 4.61 (br s, 4H, NCH2N), 4.37 (d, J = 10.8 Hz, 4H,
([Cu{DBPTA}2]+, 27), 354 ([{DBPTA} + H]+, 13).
PCH2N), 4.09–4.03 (m, 4H, NCH2N), 3.83 (br s, 4H, PCH2N),
3.59–3.5 (m, 12H, PCH2N). 31P{1H} NMR (400 MHz, CDCl3, δ):
[CuI(DBPTA)3] (4)
1
−66.77 (br s). H NMR (400 MHz, DMSO-d6, δ)/COSY: 7.46 (br
Yield = 97.1% (170 mg) based on the metal salt. Elemental s, 40H, Ar–H), 5.23 (d, 2JHH = 12.8 Hz, 4H, NCH2N), 5.00 (d, J =
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analysis calcd (%) for C57H60CuIN9O6P3: C 54.75, H 4.84, N 14.4 Hz, 4H, PCH2N), 4.77 (d, JHH = 8.4 Hz, 4H, NCH2N), 4.64
10.08; found: C 55.05, H 5.01, N 10.05. FTIR (KBr): ν (cm−1) = (d, JHH = 11.2 Hz, 4H, NCH2N), 4.23–4.14 (m, 4H NCH2N, 4H
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2918 w, 1616 s, 1575 m, 1491 w, 1404 s, 1334 s, 1241 s, PCH2N), 3.93 (d, J = 11.2 Hz, 4H, PCH2N), 3.6 (br s, 12H,
1178 m, 1126 m, 1075 s, 1027 w, 1000 s, 923 w, 882 m, 853 m, PCH2N). 31P{1H} NMR (400 MHz, DMSO-d6, δ): −63.75 (br s).
785 s, 697 s, 650 m, 507 m. 1H NMR (300 MHz, CDCl3, 13C{1H} NMR (400 MHz, DMSO-d6, δ)/DEPT/HSQC: 169.68
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δ)/COSY: 7.54–7.44 (m, 30H, Ar–H), 5.48 (d, JHH = 12 Hz, 3H, (C–O), 169.37 (C–O), 135.08 (Cquat–Ph), 129.81 (HC–Ph), 129.65
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NCH2N), 5.14 (d, J = 14.4 Hz, 3H, PCH2N), 4.9 (d, JHH = 10.5 (HC–Ph), 128.42 (HC–Ph), 128.17 (HC–Ph), 127.85 (HC–Ph),
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Hz, 3H, NCH2N), 4.59 (d, JHH = 8.7 Hz, 3H, NCH2N), 4.32 (d, 127.26 (HC–Ph), 68.1 (NCH2N), 61.67 (NCH2N), 46.12 (PCH2N),
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J = 13.8 Hz, 3H, PCH2N), 4.08 (d, JHH = 13.2 Hz, 3H, NCH2N), 44.84 (PCH2N), 37.99 (PCH2N). DEPT (400 MHz, DMSO-d6, δ):
3.84 (d, J = 12 Hz, 3H, PCH2N), 3.53 (br s, 9H, PCH2N). 31P{1H} 129.56, 129.39, 128.17, 127.92, 127.6, 127.01, 67.87, 61.41,
NMR (300 MHz, CDCl3, δ): −67.66 (br s). 13C{1H} NMR 45.87, 44.6, 37.73. ESI(+)MS in DMF (m/z assignment, % inten-
(300 MHz, CDCl3, δ)/DEPT/HSQC: 171.16 (C–O), 134.68 (Cquat
–
sity): 769 ([Cu{DBPTA}2]+, 5), 642 ([Cu2Br2{DBPTA} + H]+, 14),
Ph), 134.43 (Cquat–Ph), 130.55 (HC–Ph), 130.26 (HC–Ph), 562 ([Cu2Br{DBPTA}]+, 21), 414 ([Cu{DBPTA}]+, 67).
128.96 (HC–Ph), 128.7 (HC–Ph), 128.11 (HC–Ph), 127.56 (HC–
4.5. Synthesis of [Cu(μ-I)(DBPTA)2]2 (6)
Ph), 68.9 (NCH2N), 62.53 (NCH2N), 47.76 (PCH2N), 46.01
(PCH2N), 38.7 (PCH2N). DEPT (300 MHz, CDCl3, δ): 130.33, To an acetonitrile solution (5 mL) of CuI (26 mg, 0.14 mmol,
130.04, 128.75, 128.49, 127.90, 127.35, 68.7, 62.32, 47.59, 1 equiv.) was added an acetonitrile solution (5 mL) of 1
45.86, 38.49. 1H NMR (400 MHz, DMSO-d6, δ)/COSY: 7.45 (br s, (100 mg, 0.28 mmol, 2 equiv.) dropwise with stirring for
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30H, Ar–H), 5.24 (d, JHH = 12.8 Hz, 3H, NCH2N), 5.01 (d, J = 30 min at room temperature. The produced colourless solu-
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15.2 Hz, 3H, PCH2N), 4.77 (d, JHH = 11.6 Hz, 3H, NCH2N), tion was stirred at room temperature, and within a few
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4.65 (d, JHH = 12 Hz, 3H, NCH2N), 4.23–4.14 (m, 3H NCH2N, minutes, a white precipitate of 6 was observed. The solution
3H PCH2N), 3.91 (d, J = 13.2 Hz, 3H, PCH2N), 3.59 (m, 9H, was stirred for further 3 h, and then the resulting white
PCH2N). 31P{1H} NMR (400 MHz, DMSO-d6, δ): −65.88 (br s). product was filtered off, repeatedly washed with diethyl ether
13C{1H} NMR (400 MHz, DMSO-d6, δ)/DEPT/HSQC: 169.69 and dried in vacuum.
This journal is © The Royal Society of Chemistry 2021
Dalton Trans., 2021, 50, 6109–6125 | 6121