Ring-Opening Copolymerization of Cyclohexene Oxide and Maleic Anhydride
C
76 %). nmax (KBr)/cmꢀ1 3455 (b), 3058 (w), 2933 (w), 2862 (w),
2597 (w), 1629 (s), 1588 (m), 1470 (s), 1418 (m), 1345 (w), 1251
(vs), 1196 (w), 1168 (w), 1144 (w), 1085 (m), 1036 (w), 984 (m),
953 (w), 894 (w), 849 (m), 776 (w), 731 (m), 668 (w), 616 (w),
595 (w), 568 (w), 516 (w), 467 (w), 422 (w). dH ([D6]DMSO,
400 MHz) 13.44 (2H, s, –OH), 8.30 (2H, s, –CH¼N), 6.75 (2H, s,
–Ph), 6.67 (2H, s, –Ph), 5.94(2H, m, –CH=), 5.08 (4H, d, ¼CH2),
3.96 (4H, s, –CH2), 3.90 (6H, s, –OMe), 3.31 (4H, d, –CH2). dC
([D6]DMSO, 400MHz) 161.2, 150.6, 148.4, 137.3, 132.2, 126.5,
122.3, 117.4, 116.0, 63.7, 56.3, 48.8. Found: C 70.45, H 6.91, N
6.83. C24H28N2O4 requires C 70.50, H 6.85, N 6.86 %.
(m), 1254 (m), 1225 (m), 1161 (m), 1117 (m), 1098 (m), 1026
(w), 997 (m), 955 (w), 910 (m), 860 (w), 829(m), 762 (w), 689
(w), 650 (w), 581 (m), 555 (w), 527 (w), 471 (w), 442 (w).
Found: C 60.23, H 5.79, N 12.54. C28H32N5O4Mn requires C
60.27, H 5.74, N 12.56 %.
Synthesis of [Mn(L2)Cl] (4)
To a stirred solution of H2L2 (0.160 g, 0.35 mmol) in
absolute DMF (3 mL), a solution of Mn(OAc)2ꢁ4H2O (0.172 g,
0.70 mmol) in absolute DMF (1 mL) was added under N2
atmosphere, and the resultant mixture was stirred at ambient
temperature for 8 h. The stopper of the flask was removed, and
LiCl (76.3 mg, 1.8 mmol) was added to the solution, and the
resultant reddish brown solution was stirred at room temperature
for 24 h while exposed to dry air. The final solution was filtered
and diethyl ether was allowed to diffuse slowly into the filtrate at
room temperature and the dark brown polycrystalline solid
product of 4 was obtained in a few weeks (68.7 mg, 36 %). nmax
(KBr)/cmꢀ1 3406 (b), 2936 (m), 1659 (s), 1601 (s), 1582 (m),
1547 (s), 1493 (m), 1443 (s), 1391 (m), 1369 (m), 1317 (m), 1281
(m), 1260 (vs), 1202 (m), 1171 (m), 1119 (m), 1061 (w), 999 (s),
963 (w), 910 (m), 866 (w), 831 (m), 756 (m), 721 (w), 671 (m),
592 (m), 523 (m), 488 (w), 459 (w). Found: C 61.64, H 4.83,
N 5.10. C28H26N2O4MnCl requires C 61.67, H 4.77, N 5.14 %.
Synthesis of [Mn(L1)(OAc)] (1)
To a stirred solution of H2L1 (0.162 g, 0.35mmol) in absolute
DMF (3mL), a solutionofMn(OAc)2ꢁ4H2O (0.172 g, 0.70 mmol;
OAc ¼ CH3COO) in absolute DMF (1mL) was added under N2
atmosphere. The resultant mixture was stirred under N2 atmo-
sphere at room temperature for 8 h, and the clear brown solution
was filtered. Diethyl ether was allowed to diffuse slowly into the
filtrate at room temperature and the dark brown polycrystalline
solid product of 1 was obtained in a few weeks (87.0mg, 41 %).
n
max (KBr)/cmꢀ1 3422 (b), 2932 (m), 1618 (vs), 1551 (m), 1458
(s), 1393 (m), 1375 (m), 1346 (m), 1310 (m), 1294 (m), 1261 (s),
1229 (m), 1167 (w), 1115 (w), 1078 (w), 999 (m), 966 (w), 920
(m), 826 (m), 762 (w), 746 (w), 689 (w), 650 (w), 594 (w), 567
(w),532(w),501(w),475(w),449(w).Duetotheparamagnetism
of Mn, no NMR data could be obtained. Found: C 62.62, H 6.15,
N 4.85. C30H35N2O6Mn requires C 62.66, H 6.09, N 4.87%.
Synthesis of [Mn(L3)Cl] (5)
To a stirred solution of H2L3 (0.143 g, 0.35 mmol) in absolute
DMF (3 mL),
a
solution of Mn(OAc)2ꢁ4H2O (0.172 g,
0.70 mmol) in absolute DMF (1 mL) was added under N2
atmosphere, and the resultant mixture was stirred at ambient
temperature for 8 h. The stopper of the flask was removed, and
LiCl (76.3 mg, 1.8 mmol) was added to the solution, and the
resultant reddish brown solution was stirred at room temperature
for 24 h while exposed to dry air. The final solution was filtered
and diethyl ether was allowed to diffuse slowly into the filtrate at
room temperature and the dark brown polycrystalline solid
product of 5 was obtained in a few weeks (97.4 mg, 56 %). nmax
(KBr)/cmꢀ1 3416 (b), 2930 (m), 1628 (vs), 1551 (m), 1454 (s),
1402 (m), 1362 (m), 1344 (w), 1306 (m), 1281 (m), 1258 (s),
1206 (m), 1186 (m), 1165 (m), 1117 (m), 1090 (m), 1049 (w),
997 (s), 963 (w), 910 (m), 856 (w), 828 (m), 758 (m), 723 (w),
681 (m), 644 (m), 600 (m), 577 (w), 552 (w), 529 (w), 486 (w),
461 (w), 419 (w). Found: C 57.93, H 5.29, N 5.60.
C24H26N2O4MnCl requires C 57.96, H 5.23, N 5.64 %.
Synthesis of [Mn(L1)Cl] (2)
To a stirred solution of H2L1 (0.162 g, 0.35 mmol) in absolute
DMF (3 mL),
a
solution of Mn(OAc)2ꢁ4H2O (0.172 g,
0.70 mmol) in absolute DMF (1 mL) was added under N2
atmosphere, the resultant mixture was stirred at ambient tem-
perature for 8 h. The stopper of the flask was removed, and LiCl
(76.3 mg, 1.8 mmol) was added to the solution, and the resultant
reddish brown solution was stirred at room temperature for 24 h
while exposed to dry air. The final solution was filtered and
diethyl ether was allowed to diffuse slowly into the filtrate at
room temperature and the dark brown polycrystalline solid
product of 2 was obtained in a few weeks (113.8 mg, 59 %).
n
max (KBr)/cmꢀ1 3408 (b), 2934 (m), 1666 (s), 1628 (vs), 1553
(m), 1458 (s), 1398 (m), 1348 (m), 1314 (m), 1279 (m), 1258 (s),
1231 (m), 1169 (m), 1119 (w), 1099 (m), 1030 (w), 997 (m), 968
(w), 909 (m), 829 (m), 760 (w), 689 (w), 658 (w), 581 (m), 554
(w), 530 (w), 471 (w), 444 (w). Found: C 60.94, H 5.87, N 5.05.
C28H32N2O4MnCl requires C 60.99, H 5.81, N 5.08 %.
Structure Determination
Single crystals of complexes [Mn(L1)(OAc)] (1), [Mn(L1)Cl]
(2), [Mn(L2)Cl] (4), and [Mn(L3)Cl] (5) of suitable dimensions
were mounted onto thin glass fibres. All the intensity data were
collected on a Bruker SMART CCD diffractometer (Mo-Ka
Synthesis of [Mn(L1)N3] (3)
To a stirred solution of H2L1 (0.162 g, 0.35 mmol) in absolute
˚
radiation and l 0.71073 A) in F and v scan modes. Structures
DMF (3 mL),
a
solution of Mn(OAc)2ꢁ4H2O (0.172 g,
were solved by direct methods followed by difference Fourier
syntheses, and then refined by full-matrix least-squares techni-
ques against F2 using SHELXTL-97.[34] All other non-hydrogen
atoms were refined with anisotropic thermal parameters.
Absorption corrections were applied using SADABS.[35] All
hydrogen atoms were placed in calculated positions and refined
isotropically using a riding model.
0.70 mmol) in absolute DMF (1 mL) was added under N2
atmosphere, and the resultant mixture was stirred at ambient
temperature for 8 h. The stopper of the flask was removed, and
NaN3 (68.0 mg, 1.1 mmol) was added to the solution, and the
resulting mixture was refluxed for an additional 4 h while
exposed to dry air. The final solution was filtered and diethyl
ether was allowed to diffuse slowly into the filtrate at room
temperature and the dark brown polycrystalline solid product of
3 was obtained in a few weeks (91.8 mg, 47 %). nmax (KBr)/
cmꢀ1 3335 (b), 2930 (m), 2058 (m), 2029 (vs), 1626 (s), 1578
(s), 1551 (m), 1433 (m), 1395 (m), 1346 (m), 1310 (m), 1279
Copolymerization Procedures of CHO and MA
The copolymerization reactions between CHO and MA were
performed in both bulk and solution (toluene) with a stipulated