European Journal of Inorganic Chemistry
10.1002/ejic.201601116
FULL PAPER
1
3
36.5, 136.4, 129.9, 128.8, 126.2, 124.2, 107.4, 89.5, 87.5, 47.8, 46.1,
1.5, 23.9, 20.7, 19.7, 19.6, 18.0, 17.9, 15.4, 12.2
Acknowledgements
The authors acknowledge supports from the National Natural
Science Foundation of Zhejiang Province (LQ14B020003) and
the National Natural Science Foundation of China (81571799
and 21202147).
Synthesis of [Ru
prepared similarly as for 3a and isolated as a yellow soild. Yield: 387 mg,
2 2 2 6 2
Cl (L2)(p-cymene) ](PF ) , 3b. Complex 3b was
30%. Anal. Calcd for C44
H
56
C
l2
F
12
N
10
1
P
2
Ru
2
: C, 41.03; H, 4.38; N, 10.88.
CN): 8.20, 8.12 (both d,
Found: C, 41.28; H, 4.65; N, 10.83. H NMR (CD
3
pyridazine CH, J = 9.2 Hz, 2H), 7.98, 7.66, 7.63, 7.57 (both d, imidazole
CH, J = 2.4 Hz, 4H), 6.44, 6.24, 6.07, 5.93, 5.80, 5.34, 5.15 (both d, J =
Keywords: N-heterocyclic carbenes • Ruthenium • Pyrazole-
functionalized • Anticancer • Catalysis
6
5
2
.0 Hz, p-cymene CH, 8H), 6.37, 6.26 (both s, pyrazole CH, 2H), 5.54,
.49 (both d, CH , J = 15.2 Hz, 2H), 5.41, 4.99 (both d, CH , J = 16.0 Hz,
H), 4.71-5.65, 4.51-4.46 (both m,CH CH , 2H), 3.43 (q, J = 7.2 Hz,
CH , 2H), 2.66-2.59 (m, p-cymene CH(CH , H), 2.45-2.43 (m+s, p-
cymene CH(CH and CH , 4H), 2.33 (s, p-cymene CH , 3H), 2.14, 2.12
both s, pyrazole CH , 6H), 1.39, 1.34 (t, J = 7.2 Hz, CH CH , 6H), 1.18-
.11 (m, p-cymene CH(CH , 6H), 0.97, 0.91 (both d, J = 6.8 Hz, p-
, 6H). C NMR (CD CN): 187.5 (Ru-C), 177.7 (Ru-C),
2
2
3
2
[1]
a) M. Poyatos, J. A. Mata, E. Peris, Chem. Rev. 2009, 109, 3677-3707;
b) N. Marion, S. P. Nolan, Chem. Rev. 2009, 109, 3612-3676; c) F. E.
Hahn, M. C. Jahnke, Angew. Chem. Int. Ed. 2008, 47, 3122-3172; d) P.
G. Edwards, F. E. Hahn, Dalton Trans. 2011, 40, 10278-10288; e) S. J.
Hock, L. A. Schaper, W. A. Herrmann, F. E. Kühn, Chem. Soc. Rev.
CH
3
2
3 2
)
3
)
2
3
3
(
1
3
3
2
3 2
)
13
cymene CH(CH
3
)
2
3
2013, 42, 5073-5089; f) L. A. Schaper, S. J. Hock, W. A. Herrmann, F.
1
1
8
2
55.9, 154.5, 147.0, 145.8, 145.4, 140.7, 134.2, 126.1, 125.7, 124.4,
E. Kühn, Angew. Chem. Int. Ed. 2013, 52, 270-289.
20.2, 118.6, 113.3, 110.0, 108.1, 107.6, 105.4, 103.6, 93.0, 92.3, 90.9,
9.2, 85.8, 85.7, 85.3, 83.3, 49.5, 47.6, 45.8, 44.4, 32.0, 31.4, 24.2, 22.4,
2.1, 20.6, 19.0, 18.5, 15.3, 12.0, 10.7.
[2]
[3]
[4]
a) D. Yuan, H. Tang, L. Xiao, H. V. Huynh, Dalton Trans. 2011, 40,
Cell cytotoxicity assay. The cytotoxicity of complexes 3a, 3b, and
cisplatin against human cancer cell lines (breast cancer Bcap-37,
colorectal cancer LoVo, gastric cancer SCG7901, and cisplatin-resistant
SCG7901-R) was determined using MTT assay. The cells were plated in
a) T. Simler, P. Braunstein, A. A. Danopoulos, Chem. Commun. 2016,
2, 2717-2720; b) T. Simler, P. Braunstein, A. A. Danopoulos, Dalton
5
96-well plates (5000 cells per well) and incubated at 37°C for 24 h.
Trans. 2016, 45, 5122-5139; c) T. Simler, A. A. Danopoulos, P.
Braunstein, Chem. Commun. 2015, 51, 10699-10702; d) B. Vabre, Y.
Canac, C. Lepetit, C. Duhayon, R. Chauvin, D. Zargarian, Chem. Eur. J.
Dilutions of complexes 3a, 3b and cisplatin in DMSO were added to the
cells, and the cells were further incubated for 48 h. Subsequently, 30 µL
of MTT solution (5 mg/mL) was added to each well. The plates were
incubated at 37 °C for 4 h, allowing viable cells to reduce the yellow
tetrazolium salt into dark blue formazan crystals. After the addition of
DMSO (100 µL), the absorbance at 490 nm was determined using a
MultiSkan FC plate reader (Thermo scientific).
2015, 21, 17403-17414.
a) D. Kim, L. Le, M. J. Drance, K. H. Jensen, K. Bogdanovski, T. N.
Cervarich, M. G. Barnard, N. J. Pudalov, S. M. M. Knapp, A. R.
Chianese, Organometallics 2016, 35, 982-989; b) Z. Wang, C. Zheng,
W. Wang, C. Xu, B. Ji, X. Zhang, Inorg. Chem. 2016, 55,2157-2164; c)
A. Volpe, S. Baldino, C. Tubaro, W. Baratta, M. Basato, C. Graiff, Eur. J.
Inorg. Chem. 2016, 2, 247-251.
Wound Healing Assay. LoVo cells were grown to about 95%
confluence in a 6-well plate nearly to confluent cell monolayer. Then a
lesion was produced across the cells and washed twice with phosphate-
buffered saline (PBS). Following treatment with complex 3a (0 and 4.0
μM), the cells were photographed by microscope (magnification, × 40) at
[
5]
6]
a)M. Li, H. Song, B. Wang, J. Organomet. Chem. 2016, 804, 118-122;
b)L. Wan, D. Zhang, Organometallics 2016, 35, 138-150; c) A.
Rajaraman, A. R. Sahoo, F. Hild, C. Fischmeister, M. Achard and C.
Bruneau, Dalton Trans. 2015, 44, 17467-17472.
0
and 48h.
[
a) C. Chen, Q. Xia, H. Qiu, W. Chen, J. Organomet. Chem. 2015, 775,
103-108; b) J. C. Bernhammer, H. V. Huynh, Organometallics 2014, 33,
General procedure for oxidation of alcohols. To a dry 10 mL round-
bottom flask containing alcohol derivatives (2.0 mmol), 6.0 mmol
equivalence of hydrogen peroxide(30%) was added. This mixture was
then added by the additional 1 mol% of Ru-NHC catalysts and 3 mL
acetontrile. The reaction mixture was stirred at 60°C for 2-5 h. The
progress of the reaction was monitored by thin-layer chromatography
1266-1275; c)J. C. Bernhammer, H. V. Huynh, Organometallics 2014,
33, 172-180.
[7]
[8]
C. G. Hartinger and P. J. Dyson, Chem. Soc. Rev. 2009, 38, 391-401
B. Rosenberg, L. VanCamp, J. E. Trosko, V. H. Mansour, Nature 1969,
222, 385-386
[9]
(
TLC). After the completion of the reaction, the solution was cooled to
Am. Chem. Soc. 2015, 137, 2967-2974.
room temperature and the products were purified by flash column
chromatography eluting with petroleum ether/ethyl acetate.
[
11] a) C. Chen, H. Qiu, W. Chen, Inorg. Chem. 2011, 50, 8671-8678; b) C.
Chen, W. Chen, H. Qiu, Dalton Trans. 2012, 41, 13405-13412; c) C.
Chen, C. Lu, Q. Zheng, S. Ni, M. Zhang, W. Chen, Beilstein J. Org.
Chem. 2015, 11, 1786-1795.
X-ray diffraction analysis. Single-crystal X-ray diffraction data of 3a and
3
b (CCDC 1485263 and 1485264) were collected at 298(2) K on a
Siemens Smart-CCD area-detector diffractometer with a Mo-Kα radiation
λ= 0.71073 Å) by using a ω-2θ scan mode. Unit-cell dimensions were
obtained with least-squares refinement. Data collection and reduction
(
[12] a) B. Y. Tay, C. Wang, P. H. Phua, L. P. Stubbs, H. V. Huynh, Dalton
Trans. 2016, 45, 3558-3563; b) V. Leigh, D. J. Carleton, J. Olguin, H.
Mueller-Bunz, L. J. Wright, M. Albrecht, Inorg. Chem. 2014, 53, 8054-
8060; c) H. Ohara, W. W. N. O, A. J. Lough, R. H. Morris, Dalton Trans.
2012, 41, 8797-8808; d) L. Mercs, A. Neels, H. Stoeckli-Evans, M.
Albrecht, Inorg. Chem. 2011, 50, 8188-8196.
[
26]
were performed using the Oxford Diffraction CrysAlisPro software.
All
structures were solved by direct methods, and the non-hydrogen atoms
were subjected to anisotropic refinement by full-matrix least squares on
2
[27]
F
using the SHELXTXL package. Hydrogen atom positions for all of
the structures were calculated and allowed to ride on their respective C
atoms with C–H distances of 0.93–0.97 Å and Uiso(H) = –1.2–1.5Ueq(C).
[13] a) S. Saha, M. Kaur, K. Singh, J. K. Bera, J. Organomet. Chem. 2016,
812, 87-94; b) D. Yang, Y. Tang, H. Song, B. Wang, Organometallics
2015, 34, 2012−2017; c) X. Liu, W. Chen, Dalton Trans. 2012, 41, 599–
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