X. Chang et al. / Journal of Organometallic Chemistry 713 (2012) 134e142
141
J ¼ 6.6 Hz, eCH(CH3)2). Anal. Calcd for C50H56N6O8Pd2: C, 55.51; H,
Complex 21 was prepared in a similar way as complex 20.
5.22; N, 7.77. Found: C, 55.12; H, 5.64; N, 7.45.
3.2.19. [Pd{(4-MeO)C6H3CH]NC6H3-2,6-i-Pr2}(ONO2)]3(tpt) (21,
3.2.14. [Pd(C6H4CH]NC6H3-2,6-i-Pr2)(ONO2)]2(
m
-bpe) (16, 75%)
71%)
IR (KBr, cmꢀ1): 1603 (
n
C]N), 1384 (nNO); 1H NMR (300 MHz in
IR (KBr, cmꢀ1): 1600 ( C]N), 1384 (nNO); 1H NMR (300 MHz in
n
[d6]-DMSO,
d
): 9.01 (br, 4H, pyridyl), 8.52 (s, 2H, eCH]N), 7.93 (br,
CDCl3,
d
): 9.28 (d, 6H, J ¼ 5.4 Hz, pyridyl), 8.57 (d, 6H, J ¼ 5.7 Hz,
4H, pyridyl), 7.85 (br, 20H, eCH]CHe), 7.61 (d, 2H, J ¼ 7.2 Hz, H6),
pyridyl), 7.77 (s, 3H, eCH]N), 7.40 (d, 3H, J ¼ 8.1 Hz, H6), 7.30 (dd,
0
0
0
0
0
7.41 (t, 2H, J ¼ 7.2 Hz, H4 ), 7.33 (d, 4H, J ¼ 7.2 Hz, H3 , H5 ), 7.23 (t, 2H,
J ¼ 7.2 Hz, H5), 7.15 (dd, 2H, J ¼ 8.1, 7.8 Hz, H4), 6.28 (br, 2H, H3), 3.42
(m, 4H, eCH(CH3)2), 1.39 (d, 12H, J ¼ 6.6 Hz, eCH(CH3)2), 1.18 (d,
3H, J ¼ 7.8, 7.8 Hz, H4 ), 7.19 (d, 6H, J ¼ 7.8 Hz, H3 , H5 ), 6.68 (d, 3H,
J ¼ 8.1 Hz, H5), 5.91 (s, 3H, H3), 3.69 (s, 9H, eOCH3), 3.57 (hepta, 6H,
eCH(CH3)2), 1.45 (d, 18H, J ¼ 6.6 Hz, eCH(CH3)2), 1.19 (d, 18H,
J ¼ 6.9 Hz, eCH(CH3)2). Anal. Calcd for C78H84N12O12Pd3$CH2Cl2: C,
53.13; H, 4.85; N, 9.41. Found: C, 53.29; H, 5.28; N, 9.28.
12H,
J ¼ 6.6 Hz,
eCH(CH3)2).
Anal.
Calcd
for
C50H54N6O6Pd2$0.75CH2Cl2: C, 54.84; H, 5.03; N, 7.56. Found: C,
54.92; H, 4.88; N, 7.49.
3.3. X-ray structure determination
3.2.15. [Pd{(4-MeO)C6H3CH]NC6H3-2,6-i-Pr2}(ONO2)]2(
m-bpe)
(17, 78%)
Suitablecrystals for X-rayanalysis of3, 9,13 and 21 wereobtained
by recrystallization from CH2Cl2/hexane. X-ray data of complexes 3,
9,13 and 21 were collected on a D-MAX 2200 VPC diffractometer. All
IR (KBr, cmꢀ1): 1600 ( C]N), 1384 (nNO); 1H NMR (300 MHz [d6]-
n
DMSO, d): 9.00 (br, 4H, pyridyl), 8.34 (s, 2H, eCH]N), 7.93 (br, 4H,
pyridyl), 7.86 (br, 2H, eCH]CHe), 7.58 (d, 2H, J ¼ 8.4 Hz, H6), 7.39
the determinations of unit cell and intensity data were performed
0
0
0
(dd, 2H, J ¼ 8.4, 6.9 Hz, H4 ), 7.31 (d, 4H, J ¼ 7.5 Hz, H3 , H5 ), 6.80 (d,
2H, J ¼ 8.4 Hz, H5), 5.67 (br, 2H, H3), 3.68 (s, 6H, eOCH3), 3.45 (m,
4H, eCH(CH3)2), 1.37 (d, 12H, J ¼ 6.6 Hz, eCH(CH3)2), 1.17 (d, 12H,
J ¼ 6.6 Hz, eCH(CH3)2). Anal. Calcd for C52H58N6O8Pd2$0.5CH2Cl2:
C, 54.81; H, 5.17; N, 7.31. Found: C, 54.73; H, 4.98; N, 7.04.
ꢀ
with graphite-monochromated Mo K
a
radiation (
l
¼ 0.71073 A).
The data of complexes 3 and 13 were collected at room temperature
while the data of complex 9 and 21 were collected at 113 K using the
u
-scan technique. Details of the data collection and refinement are
summarized in Table 1. All calculations were carried out with the
SHELX-97 programs [44]. All structures were solved by direct
methods. All non-hydrogen atoms were refined with anisotropic
thermal parameters by using full-matrix least-squares methods.
3.2.16. [Pd(C6H4CH]NC6H3-2,6-i-Pr2)(ONO2)]2(
m-bpt) (18, 79%)
IR (KBr, cmꢀ1): 1602 ( C]N), 1384 (nNO); 1H NMR (300 MHz in
n
CDCl3,
d
): 9.17 (d, 4H, J ¼ 6.3 Hz, pyridyl), 8.09 (d, 4H, J ¼ 6.3 Hz,
pyridyl), 7.88 (s, 2H, eCH]N), 7.45 (d, 2H, J0¼ 7.2 Hz, H6), 7.31 (dd,
Acknowledgment
0
0
2H, J ¼ 7.2, 7.2 Hz, H4 ), 7.17e7.22 (m, 6H, H3 , H5 , H5), 7.09 (dd, 2H,
J ¼ 7.5, 7.5 Hz, H4), 6.39 (d, 2H, J ¼ 7.5 Hz, H3), 3.52 (hepta, 4H,
eCH(CH3)2), 1.44 (d, 12H, J ¼ 6.6 Hz, eCH(CH3)2), 1.18 (d, 12H,
This work was supported by the Project Sponsored by the
Scientific Research Foundation for the Returned Overseas Chinese
Scholars of State Education Ministry (2008), the Scientific Research
Foundation funded by Liaoning Provincial Education Department of
China [No. 2008T073], the Natural Science Foundation of Liaoning
Province [No. 201102085], and Foundation of 211 Project for
Innovative Talents Training, Liaoning University.
J ¼ 6.9 Hz,
eCH(CH3)2).
Anal.
Calcd
for
C50H52N8O6Pd2S$0.25CH2Cl2: C, 53.55; H, 4.69; N, 9.94; S, 2.84.
Found: C, 53.58; H, 4.81; N, 10.03, S, 3.03. ESI-MS: m/z ¼ 1106.5
(MHþ). C50H52N8O6Pd2S (Mr ¼ 1105.9).
3.2.17. [Pd{(4-MeO)C6H3CH]NC6H3-2,6-i-Pr2}(ONO2)]2(
m-bpt)
(19, 56%)
Appendix A. Supporting material
IR (KBr, cmꢀ1): 1599 ( C]N), 1384 (nNO); 1H NMR (300 MHz in
n
[d6]-DMSO, d): 9.13 (br, 4H, pyridyl), 8.35 (s, 2H, eCH]N), 8.28 (br,
CCDC 842514e842517 contains the supplementary crystallo-
graphic data for 3, 9, 13 and 21. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via www.
4H, pyridyl), 7.58 (d, 2H, J ¼ 8.4 Hz, H6), 7.40 (dd, 2H, J ¼ 7.8, 7.2 Hz,
0
0
0
H4 ), 7.32 (d, 4H, J ¼ 7.2 Hz, H3 , H5 ), 6.82 (d, 2H, J ¼ 8.4 Hz, H5), 5.76
(s, 2H, H3), 3.72 (s, 6H, eOCH3), 3.46 (hepta, 4H, eCH(CH3)2), 1.37 (d,
12H, J ¼ 6.3 Hz, eCH(CH3)2), 1.16 (d, 12H, J ¼ 6.6 Hz, eCH(CH3)2).
Anal. Calcd for C52H56N8O8Pd2S$0.5CH2Cl2: C, 52.18; H, 4.75; N,
9.27. Found: C, 51.88; H, 4.66; N, 7.04.
References
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3.2.18. [Pd(C6H4CH]NC6H3-2,6-i-Pr2)(ONO2)]3(tpt) (20)
To
a 15 mL CH2Cl2 suspension of complex 11 (0.103 g,
0.067 mmol) was added AgNO3 (0.044 g, 0.259 mmol) solution
dissolved in 5 mL methanol. After stirring for 10 h in dark at room
temperature, insoluble materials were filtered off, the filtrate was
evaporated to remove the solvents. The residue was isolated with
ether giving a yellowish green solid. After recrystallization from
CH2Cl2/hexane yellowish green crystals of [Pd3(C6H4CH]NC6H3-
2,6-i-Pr2)3(tpt)(ONO2)3] (20, 0.071 g, 66%) were obtained. IR (KBr,
cmꢀ1): 1602 ( C]N), 1384 (nNO); 1H NMR (300 MHz in CDCl3,
n d):
9.28 (d, 6H, J ¼ 6.6 Hz, pyridyl), 8.61 (d, 6H, J ¼ 6.6 Hz, pyridyl), 7.90
40
(s, 3H, eCH]N), 7.46 (d, 3H, J ¼ 7.2 Hz, H6), 7.29e7.34 (m, 3H, H ),
0
0
7.17e7.22 (m, 9H, H3 , H5 , H5), 7.05e7.11 (m, 3H, H4), 6.41 (d, 3H,
J ¼ 7.2 Hz, H3), 3.55 (hepta, 6H, eCH(CH3)2), 1.45 (d, 18H, J ¼ 6.6 Hz,
eCH(CH3)2), 1.19 (d, 18H, J ¼ 6.6 Hz, eCH(CH3)2). Anal. Calcd for
C75H78N12O9Pd3$0.5CH2Cl2: C, 54.85; H, 4.82; N, 10.17. Found: C,
54.73; H, 5.11; N, 10.11.
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