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M.-C. Wu et al. / Journal of Organometallic Chemistry 791 (2015) 141e147
using an aqueous NaOH solution, extracted with diethyl ether, and
dried over anhydrous MgSO4 to obtain 0.94 g of final product 1 (87%
yield). 1H NMR (CDCl3)：2.61 (m, 4H, CH2), 3.20 (m, 4H, CH2), 3.57
(s, 2H, CH2), 6.08 (m, 1H, CH pyr), 6.14 (m, 1H, CH pyr), 6.76 (m, 1H,
CH pyr), 6.84 (m, 1H, CH ph), 6.90 (m, 2H, CH ph), 7.27 (m, 2H, CH
ph), 8.72 (br, 1H, NH). 13C NMR (CDCl3):49.1 (t, JCH ¼ 136 Hz, CH2),
53.1 (t, JCH ¼ 132 Hz, CH2), 55.5 (t, JCH ¼ 133 Hz, CH2), 108.0 (d,
JCH ¼ 175 Hz, CH pyr), 108.1 (d, JCH ¼ 178 Hz, CH pyr), 116.2 (d,
JCH ¼ 158 Hz, CH ph), 117.9 (d, JCH ¼ 184 Hz, CH pyr), 119.9 (d,
JCH ¼ 160 Hz, CH ph), 127.9 (s, Cipso pyr), 129.3 (d, JCH ¼ 160 Hz, CH
ph), 151.3 (s, Cipso ph).
ZnMe{C4H2N-{2,5-[CH2N(CH2CH2)2NPh]2}} (5)
ZnMe2 (1.2 M in toluene, 0.66 mL, 0.79 mmol) was added to a
flask containing 2 (0.30 g, 0.72 mmol) and 40 mL of toluene via
syringe at ꢀ78 ꢁC. The solution was stirred at room temperature for
1 h, and the volatile compounds were removed under vacuum to
yield an off-white powder (0.12 g, 34.0% yield). 1H NMR
(CDCl3): ꢀ0.35 (s, 3H, ZnCH3), 2.73 (br, 8H, CH2), 3.23 (br, 8H, CH2),
3.60 (s, 4H, CH2), 6.00 (s, 2H, CH pyr), 6.85e6.92 (m, 6H, CH ph),
7.19e7.29 (m, 4H, CH ph). 13C NMR (CDCl3): ꢀ8.7 (q, JCH ¼ 122 Hz,
ZnCH3), 48.8 (t, JCH ¼ 136 Hz, CH2), 53.6 (t, JCH ¼ 135 Hz, CH2), 76.7
(t, JCH ¼ 135 Hz, CH2), 105.8 (d, JCH ¼ 167 Hz, CH pyr), 116.4 (d,
JCH ¼ 159 Hz, CH ph), 120.2 (d, JCH ¼ 161 Hz, CH ph), 129.3 (d,
JCH ¼ 158 Hz, CH ph), 134.3 (s, Cipso pyr), 151.0 (s, Cipso ph). Calcd
[C27H35N5Zn]: C, 64.65; H, 7.05; N, 13.91. Found: C, 65.06; H, 7.25; N,
13.52.
C4H2NH-{2,5-[CH2N(CH2CH2)2NPh]2} (2)
A similar procedure was used as in the synthesis of compound 1.
Phenylpiperazine 4.92 g (25.0 mmol), formaldehyde (37%, 2.42 g,
25.0 mmol), and pyrrole (1.0 g, 25.0 mmol) were used and 4.42 g of
final product was obtained (71.3% yield). 1H NMR (CDCl3): 2.58 (m,
8H, CH2), 3.18 (m, 8H, CH2), 3.52 (s, 4H, CH2), 5.95 (s, 2H, CH pyr),
6.84 (m, 2H, CH ph), 6.90 (m, 4H, CH ph), 7.25 (m, 4H, CH ph), 8.77
(br, 1H, NH).13C NMR (CDCl3): 49.1 (t, JCH ¼ 135 Hz, CH2), 53.0 (t,
JCH ¼ 134 Hz, CH2), 55.5 (t, JCH ¼ 134 Hz, CH2), 107.8 (d, JCH ¼ 171 Hz,
CH pyr),116.1 (d, JCH ¼ 155 Hz, CH ph),119.8 (d, JCH ¼ 160 Hz, CH ph),
128.1 (s,Cipso pyr), 130.2 (d, JCH ¼ 150 Hz,CH ph), 151.3 (s,Cipso ph).
Calcd [C26H33N5]: C, 71.52; H, 7.67; N,15.88. Found: C, 71.13; H, 7.58;
N, 15.66.
Zn{C4H2N-{2,5-[CH2N(CH2CH2)2NPh]2}}2 (6)
ZnMe2 (1.2 M in toluene, 0.50 mL, 0.60 mmol) was added to a
flask containing 2 (0.50 g, 1.2 mmol) and 40 mL of toluene via sy-
ringe at room temperature. The solution was heated at 60 ꢁC for 3 h,
and the volatile compounds were removed under vacuum to yield a
pale pink solid (0.95 g, 82.0% yield). Crystals of 6 were obtained
from a saturated toluene solution at ꢀ20 ꢁC. 1H NMR (CDCl3): 2.82
(m, 16H, CH2), 3.20 (m, 16H, CH2), 3.61 (s, 8H, CH2), 6.08 (s, 4H, CH
pyr), 6.87 (m, 12H, CH ph), 7.27 (m, 8H, CH ph). 13C NMR (CDCl3):
48.7 (t, JCH ¼ 135 Hz, CH2), 54.2 (t, JCH ¼ 135 Hz, CH2), 59.5 (t,
JCH ¼ 134 Hz, CH2), 107.4 (d, JCH ¼ 168 Hz, CH pyr), 116.3 (d,
JCH ¼ 154 Hz, CH ph), 120.2 (d, JCH ¼ 161 Hz, CH ph), 129.3 (d,
JCH ¼ 158 Hz, CH ph), 133.6 (s, Cipso pyr), 150.9 (s, Cipso ph). Calcd
[C52H64N10Zn]: C, 67.78; H, 7.03; N, 15.08. Found: C, 68.19; H, 6.74;
N, 14.66.
{ZnMe{C4H3N-[2-CH2N(CH2CH2)2NPh]}}2 (3)
ZnMe2 (1.2 M in toluene, 0.76 mL, 0.91 mmol) was added to a
flask containing 1 (0.20 g, 0.83 mmol) and 10 mL of toluene via
syringe at room temperature. The solution was stirred at room
temperature for 3 h, and the volatile compounds were removed
under vacuum to yield a pale yellow solid (0.37 g, 78.0% yield).
Crystals of 3 were obtained from a saturated methylene chloride
solution at ꢀ20 ꢁC. 1H NMR (CDCl3): ꢀ0.39 (s, 6H, ZnCH3), 2.59 (m,
4H, CH2), 3.12 (m, 8H, CH2), 3.54 (m, 4H, CH2), 3.98 (s, 4H, CH2), 6.12
(s, 2H, CH pyr), 6.27 (s, 2H, CH pyr), 6.85 (s, 2H, CH pyr), 6.91 (m, 6H,
CH ph), 7.30 (m, 4H, CH ph). 13C NMR (CDCl3): ꢀ9.6 (q, JCH ¼ 121 Hz,
ZnCH3), 48.1 (t, JCH ¼ 136 Hz, CH2), 54.5 (t, JCH ¼ 137 Hz, CH2), 59.1 (t,
JCH ¼ 137 Hz, CH2), 105.7 (d, JCH ¼ 167 Hz, CH pyr), 109.5 (d,
JCH ¼ 166 Hz, CH pyr), 116.5 (d, JCH ¼ 155 Hz, CH ph), 120.7 (d,
JCH ¼ 160 Hz, CH ph), 126.5 (d, JCH ¼ 179 Hz, CH pyr), 129.4 (d,
JCH ¼ 158 Hz, CH ph), 135.4 (s, Cipso pyr), 150.5 (s,Cipso ph). Calcd
[C32H42N6Zn2]: C, 57.61; H, 6.38; N, 12.44. Found: C, 57.63; H, 6.60;
N, 12.51.
X-ray structure determination for compounds 1, 3, 4, 6, and 7
All of the crystals were mounted on a glass fiber using epoxy
resin and transferred to a goniostat. The data were collected on a
Bruker SMART CCD diffractometer using graphite monochromated
Mo-Ka radiation. The data were corrected for absorption empiri-
cally via
j scans. All non-hydrogen atoms were refined using
anisotropic displacement parameters. For all of the structures, the
hydrogen atom positions were calculated, and they were con-
strained to idealized geometries and treated as riding where the H
atom displacement parameter was calculated from the equivalent
isotropic displacement parameter of the bound atom. The struc-
tures were determined using direct-method procedures in SHELXS
[79] and refined using full-matrix least-squares methods on F2's in
SHELXL [80].
{Zn(m-O-C6H4-4-Me){C4H3N-[2-CH2N(CH2CH2)2NPh]}}2 (4)
A one-pot reaction was used for the synthesis of compound 4.
After synthesizing compound 3 using 1 (0.20 g, 0.83 mmol) and
ZnMe2 (1.2 M in toluene, 0.76 mL, 0.91 mmol), a toluene (10 mL)
solution of p-cresol (0.081 g, 0.075 mmol) was added, and the so-
lution was stirred for 12 h. The volatile compounds were removed
under vacuum, and the solid was recrystallized from a saturated
methylene chloride solution at ꢀ20 ꢁC to yield colorless crystals of
4 (0.18 g, 28.8% yield). 1H NMR (CDCl3): 2.22 (s, 6H, CH3), 2.59 (m,
4H, CH2), 2.96 (m, 8H, CH2), 3.42 (m, 4H, CH2), 3.83 (s, 4H, CH2), 6.20
(m, 2H, CH pyr), 6.30 (m, 2H, CH pyr), 6.63 (m, 2H, CH pyr),
6.56e7.31 (m, 18H, CH ph). 13C NMR (CDCl3): 20.6 (q, JCH ¼ 131 Hz,
CH3), 49.2 (t, JCH ¼ 135 Hz, CH2), 54.7 (t, JCH ¼ 138 Hz, CH2), 50.3 (t,
JCH ¼ 138 Hz, CH2), 105.1 (d, JCH ¼ 165 Hz, CH pyr), 109.4 (d,
JCH ¼ 166 Hz, CH pyr), 117.0 (d, JCH ¼ 155 Hz, CH ph), 117.5 (d,
JCH ¼ 157 Hz, CH ph), 121.4 (d, JCH ¼ 156 Hz, CH ph), 126.1 (d,
JCH ¼ 180 Hz, CH pyr), 129.4 (d, JCH ¼ 158 Hz,CH ph), 130.8 (d,
JCH ¼ 161 Hz,CH ph), 133.1 (s, Cipso pyr), 150.4 (s, Cipso ph), 157.2 (s,
Cipso ph). Calcd [C44H50N6Zn2O2.CH2Cl2]: C, 59.35; H, 5.76; N, 9.22.
Found: C, 59.01; H, 5.73; N, 8.80.
The crystallographic data for the structures reported in this
paper have been deposited with the Cambridge Crystallographic
Data Centre as supplementary publications nos. CCDCC-995603 (1),
CCDC-995604 (2), CCDC-995605 (3), CCDC-995606 (4), and CCDC-
995607 (6) and CCDC-995608 (7). These data can be obtained
free of charge from The Cambridge Crystallographic Data Centre via
Polymerization
In a typical procedure, the initiator was first dissolved in 30 mL
of toluene followed by the addition of ε-caprolactone and then
stirred at 30 ꢁC for 24 h to produce a gel- or solid-like polymer. The
mixture was gradually quenched with distilled water, and the
resulting solid was washed with hexane and methanol. It was dried
and gave a satisfactory yield. The molecular weight of the polymers
was determined using a gel permeation chromatography (GPC)
instrument (Waters, RI 2414, pump 1515).
Wu, Ming-Chun
