Page 7 of 9
RSC Advances
DOI: 10.1039/C4RA13017K
8: blue solid. m.p. = 158 °C. 1H NMR (CDCl3): δ 3.82 (s, 3H, O–
Notes and references
CH3), 4.37 (s, 1H, S–CH), 5.02 (s, 5H, Cp), 11B NMR (CDCl3): δ
−7.93 (2B), −6.55 (2B), −4.89 (1B), −2.20 (3B), −1.17 (2B), 13C
NMR (CDCl3): δ 45.03 (S–CH), 52.80 (O–CH3), 85.01 (Cp),
88.49 (Carborane), 92.81 (Carborane), 175.19 (O=C). ESI−MS
(70 eV): m/z 392.33 ([M]−, 60%). IR (KBr): ν (cm−1) 1697(C=O),
2596 (B−H). Anal. Calcd (%) for C10H19B10CoO2S2: C, 29.85; H,
4.76. Found: C, 29.99; H, 4.95.
60 a State Key Laboratory of Coordination Chemistry, School of Chemistry
and Chemical Engineering, Nanjing University, Nanjing, Jiangsu 210093,
China. Tel: +86ꢀ25ꢀ83686724; Eꢀmail: hyan1965@nju.edu.cn
b College of Biological, Chemical Sciences and Engineering, Jiaxing
University, Jiaxing, Zhejiang 314001, China. Tel: +86ꢀ573ꢀ83640303
5
65
1
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Synthesis of 10. Method 1. Toluenesulphonyl azide (59.1 mg, 0.3
2
3
P. S. Hanley and J. F. Hartwig, Angew. Chem. Int. Ed., 2013, 52,
8510ꢀ8525.
10 mmol) was added to the blue solution of 8 (80.6 mg, 0.2 mmol) in
toluene (20 mL). The mixture was heated at 90 C for 6 h. The
o
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colour gradually turned from blue to purple. After removal of the
solvent, the residue was chromatographically separated on silica,
and elution with petroleum ether/DCM gave 10 (67 mg, 57%).
15 Method 2. Complex 9 was prepared according to our recent
work.18m The solution of 9 (105.4 mg, 0.2 mmol) in DCM
(20mL) was added with methyl diazoacetate (2.76 M in solution
of 1, 2ꢀdichloroethane, 41.4 mg in 0.15 mL). The mixture was
stirred for 6 h at ambient temperature. The colour gradually
20 turned from green to purple. After removal of the solvent, the
residue was chromatographically separated on silica, and elution
with petroleum ether/DCM gave 10 (69 mg, 59%).
4
5
6
75
7
80
10: purple solid. m.p. = 117 °C. 1H NMR (CDCl3): δ 2.43 (s, 3H,
Ph–CH3), 3.91 (s, 3H, O–CH3), 4.05 (s, 1H, S–CH), 5.14 (s, 5H,
25 Cp), 7.29 (d, 2H, J = 8.0 Hz, Ph), 7.76 (d, 2H, J = 9.0 Hz, Ph),
11B NMR (CDCl3): δ −12.25 (1B), −10.27 (1B), −9.01 (2B),
−7.84 (1B), −6.07 (1B), −2.96 (1B), 0.87 (1B), 2.81 (2B), 13C
NMR (CDCl3): δ 21.48 (Ph–CH3),43.27 (S–CH), 53.03 (O–CH3),
57.38 (Carborane), 85.17 (Cp), 86.06 (Carborane), 127.84
30 (2×Ph), 129.32 (2×Ph), 137.69 (Ph), 143.01 (Ph), 175.59 (O=C).
ESI−MS (70 eV): m/z 573 ([M+H]+, 60 %), 595 ([M+Na]+,
100%). IR (KBr): ν (cm−1) 1707 (C=O), 2579 (B−H). Anal. Calcd
(%) for C17H26B10CoNO4S3: C, 35.72; H, 4.58; N, 2.45. Found:
C, 35.88; H, 4.86; N, 2.59.
35 Xꢀray Structure Determinations. Crystals suitable for Xꢀray
analysis were obtained by the slow evaporation of a solution in
petroleum ether/dichloromethane. Diffraction data were collected
on a Bruker SMART Apex II CCD diffractometer by means of
graphitemonochromated Mo–Kα (λ = 0.71073 Å) radiation.
40 During collection of the intensity data, no significant decay was
observed. The intensities were corrected for Lorentz polarization
effects and empirical absorption by using the SADABS
program.28 The structures were solved by direct methods with the
SHELXSꢀ97 program29 and were refined on F2 with SHELXTL
45 (version 6.14).30 All nonꢀhydrogen atoms were refined
anisotropically. Hydrogen atoms were included in calculated
positions and were refined using a riding model. A summary of
crystal data, data collection parameters, and structure refinement
details is given in Tables 1 and 2. CCDC 1009704–1009710 for
50 the complexes 3−8 and 10 contain the supplementary
crystallographic data for this paper. These data can be obtained
85
8
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free of charge from The Cambridge Crystallographic Data Centre 120
55 Acknowledgements
This work was supported by the National Basic Research
Program of China (2013CB922101), the Natural Science
Foundation of China (21271102 and 21301071).
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