Paper
RSC Advances
CH3ortho). 13C NMR (100 MHz, DMSO-d6): d ¼ 149.14 (C]Se),
139.85, 134.57, 132.94, 129.53, 123.31 (ArC), 20.77 (p-CH3), 17.38
(o-CH3). FT-IR (neat): ꢀn ¼ 3143(w), 3107(w), 3079(w), 2913(m),
1599(m), 1551(m), 1477(s), 1443(m), 1369(s), 1334(w), 1289(m),
1228(s), 1163(w) (C]Se), 1123(m), 1026(m), 922(w), 849(s),
Synthesis of 2
Complex 2 was prepared in the same manner as described for 1
using IMes]S (0.100 g, 0.297 mmol) and CuBr (0.051 g, 0.356
mmol) in methanol (5 mL). Yield: 84% (based on CuBr). Mp:
220–222 ꢁC (decomposed). Elemental analysis calcd (%) for
746(s), 684(s), 599(w), 566(m) cmꢀ1
.
C
21H24BrCuN2S (479.93): C, 52.55; H, 5.04; N, 5.84; found: C,
52.54; H, 5.07; N, 5.79. 1H NMR (400 MHz, DMSO-d6): d ¼ 7.31
(s, 2H, ImH), 6.97 (s, 4H, CHmeta), 2.22 (s, 6H, CH3para), 1.93 (s,
12H, CH3ortho). 13C NMR (100 MHz, DMSO-d6): d ¼ 159.87 (C]
S), 138.59, 135.02, 133.21, 128.87, 119.70 (ArC), 20.62 (p-CH3),
17.32 (o-CH3). FT-IR (neat): ꢀn ¼ 3147(w), 3113(w), 3084(w),
2916(m), 1604(m), 1556(w), 1481(s), 1449(m), 1382(s), 1345(w),
1289(m), 1234(s), 1167(w) (C]S), 1141(w), 1033(m), 924(w),
885(s), 851(m), 748(s), 693(s), 644(w), 605(m), 573(m),
Synthesis of 7
Method 1. Complex 7 can be prepared in the same manner as
described for 1 using IMes]Se (0.100 g, 0.260 mmol) and CuCl
(0.031 g, 0.312 mmol) in methanol (5 mL). Yield: 75% (based on
CuCl).
Method 2. IMes]Se (0.100 g, 0.260 mmol) was treated with
excess [(IMes)CuCl] (0.16 g, 0.426 mmol) in acetone under
reuxing conditions overnight to yield 7. Yield: 65% (based on
IMesCuCl). Mp: 218–220 ꢁC (melting). Elemental analysis calcd
(%) for C42H48Cl2Cu2N4Se2 (964.79): C, 52.29; H, 5.01; N, 5.81;
found: C, 52.30; H, 5.07; N, 5.84. 1H NMR (400 MHz, DMSO-d6):
d ¼ 7.81 (s, 2H, ImH), 7.07 (s, 4H, CHmeta), 2.28 (s, 6H, CH3para),
1.94 (s, 12H, CH3ortho). 13C NMR (100 MHz, DMSO-d6): d ¼
148.59 (C]Se), 140.00, 134.46, 132.76, 129.58, 123.45 (ArC),
20.74 (p-CH3), 17.21 (o-CH3). FT-IR (neat): ꢀn ¼ 3146(w), 3106(w),
3076(w), 2915(m), 1607(m), 1553(w), 1482(s), 1448(m), 1371(s),
1338(m), 1292(m), 1233(s), 1165(w) (C]Se), 1125(w), 1033(s),
519(m) cmꢀ1
.
Synthesis of 3
A mixture of IMes]S (0.100 g, 0.297 mmol) and CuI (0.068 g,
0.356 mmol) in methanol (5 mL) was reuxed at 80 ꢁC for 12 h.
The resulting white precipitate was dissolved in hot acetonitrile
and allowed to crystallize under ambient conditions over 2 days.
Yield: 71% (based on CuI). Mp: 232–234 ꢁC (melting). Elemental
analysis calcd (%) for C21H24CuIN2S (526.95): C, 47.87; H,
1
4.59; N, 5.32; found: C, 47.84; H, 4.57; N, 5.29. H NMR (400
925(w), 852(s), 754(s), 688(s), 595(s), 569(s) cmꢀ1
.
MHz, DMSO-d6): d ¼ 7.61 (s, 2H, ImH), 7.08 (s, 4H, CHmeta), 2.28
(s, 6H, CH3para), 1.98 (s, 12H, CH3ortho). 13C NMR (100 MHz,
DMSO-d6): d ¼ 156.55 (C]S), 139.76, 134.78, 132.17, 129.50,
121.27 (ArC), 20.69 (p-CH3), 17.23 (o-CH3). FT-IR (neat): ꢀn ¼
3145(w), 3111(w), 3084(w), 2913(m), 1597(m), 1556(w), 1478(s),
1445(m), 1380(s), 1286(m), 1230(s), 1165(w) (C]S), 1138(w),
Synthesis of 8
Complex 8 can be prepared as a by-product during the synthesis
of 7 in method 2. Yield: 30% based on [(IMes)CuCl]. Mp: 277–
279 ꢁC (decomposed). Elemental analysis calcd (%) for C42-
H48ClCuN4 (707.85): C, 71.26; H, 6.83; N, 7.91; found: C, 71.30;
1028(m), 921(w), 848(s), 743(s), 690(s), 604(m), 570(m) cmꢀ1
.
1
H, 6.87; N, 7.94. H NMR (400 MHz, CDCl3): d ¼ 7.00 (s, 4H,
ImH), 6.89 (s, 8H, CHmeta), 2.41 (s, 12H, CH3para), 1.66 (s, 24H,
CH3ortho). 13C NMR (100 MHz, CDCl3): d ¼ 177.35 (C–Cu),
139.39, 134.53, 134.45, 129.16, 122.78 (ArC), 21.18 (p-CH3), 16.95
(o-CH3). FT-IR (neat): ꢀn ¼ 2912(m), 1604(m), 1542(w), 1483(s),
1400(m), 1266(s), 1230(s), 1163(m), 1069(m), 1036(m), 929(m),
Synthesis of 4
Complex 4 was prepared in the same manner as described for 1
using IMes]Se (0.100 g, 0.260 mmol) and CuBr (0.048 g, 0.312
mmol) in methanol (5 mL). Yield: 87% (based on CuBr). Mp:
ꢁ
857(s), 733(s), 641(m), 573(m) cmꢀ1
.
227–229 C (melting). Elemental analysis calcd (%) for C21H24-
BrCuN2Se (526.85): C, 47.88; H, 4.59; N, 5.32; found: C, 47.91; H,
1
4.57; N, 5.29. H NMR (400 MHz, DMSO-d6): d ¼ 7.73 (s, 2H,
Synthesis of 9
ImH), 7.02 (s, 4H, CHmeta), 2.25 (s, 6H, CH3para), 1.95 (s, 12H,
CH3ortho). 13C NMR (100 MHz, DMSO-d6): d ¼ 148.22 (C]Se),
139.24, 134.58, 133.32, 129.13, 123.30 (ArC), 20.68 (p-CH3), 17.57
(o-CH3). FT-IR (neat): ꢀn ¼ 3145(w), 3108(w), 3078(w), 2916(m),
1605(m), 1553(w), 1480(s), 1447(m), 1371(s), 1337(w), 1291(m),
1232(s), 1166(w) (C]Se), 1125(w), 1032(m), 925(w), 851(s),
Method 1. Complex 9 can be prepared in the same manner as
described for 1 using IMes]Se (0.100 g, 0.260 mmol) and
[Cu(CH3CN)4]PF6 (0.097 g, 0.260 mmol) in methanol (5 mL).
Yield: 80% (based on [Cu(CH3CN)4]PF6).
Method 2. IMes]Se (0.100 g, 0.260 mmol) was treated with
[(IMes)CuCl] (0.208 g, 0.520 mmol) and an excess of KPF6
(0.239 g, 1.300 mmol) in acetone under reuxing conditions
overnight to yield the desired product 9. Yield: 68% (based on
[(IMes)CuCl]. Mp: 259 ꢁC (decomposed). Elemental analysis
752(s), 688(s), 594(w), 568(s), 520(m) cmꢀ1
.
Synthesis of 5
Complex 5 was prepared in the same manner as described for 3 calcd (%) for C42H48CuF6N4PSe2 (975.28): C, 51.72; H, 4.96; N,
using IMes]Se (0.100 g, 0.260 mmol) and CuI (0.060 g, 0.312 5.74; found: C, 51.73; H, 4.97; N, 5.80. 1H NMR (400 MHz,
mmol) in methanol (5 mL). Yield: 77% (based on CuI). Mp: 224– CDCl3): d ¼ 7.36 (s, 4H, ImH), 7.04 (s, 8H, CHmeta), 2.37 (s, 12H,
226 ꢁC (melting). Elemental analysis calcd (%) for C21H24
-
CH3para), 2.10 (s, 24H, CH3ortho). 13C NMR (100 MHz, CDCl3): d ¼
CuIN2Se (573.85): C, 43.95; H, 4.22; N, 4.88; found: C, 43.91; H, 142.28 (C]Se), 140.96, 134.70, 132.53, 129.88, 124.58 (ArC),
1
4.17; N, 4.89. H NMR (400 MHz, DMSO-d6): d ¼ 7.79 (s, 2H, 21.35 (p-CH3), 18.47 (o-CH3). 31P NMR (CDCl3, 161 MHz):
ImH), 7.08 (s, 4H, CHmeta), 2.30 (s, 6H, CH3para), 1.97 (s, 12H, ꢀ157.59 to ꢀ131.22 (sept, PF6). 19F NMR (CDCl3, 376 MHz):
This journal is © The Royal Society of Chemistry 2018
RSC Adv., 2018, 8, 32269–32282 | 32271