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New Journal of Chemistry
Page 7 of 9
DOI: 10.1039/C8NJ03706J
Journal Name
ARTICLE
cyclopentylꢀCH2), 1.97ꢀ1.83 (m, 2H, cyclopentylꢀCH2), 1.72ꢀ Al2O3 and further identified by comparison with authentic
1.56 (m, 2H, cyclopentylꢀCH2) ppm. 13C NMR(125 MHz, sample through NMR.
CDCl3, 298 K):δ 206.4, 204.0, 203.1, 199.4, 197.1, 196.9, X-ray Crystal Structural Determination. Single crystals of
193.2, 189.9, 185.2, 169.7, 146.7, 138.8, 128.6, 118.3, 101.8, complexes 1a-1d (CCDC 1838366, 1576322, 1838365,
46.2, 44.6, 25.2, 24.4 ppm. IR(υCO, KBr, cmꢀ1): 2093 (s), 2059 1573451) suitable for Xꢀray diffraction were obtained by
(s), 2023 (s), 1998 (s), 1975 (s), 1929 (s).
Complex 1b. Complex 1b was synthesized following with the
analogous methods as described above for the synthesis of SMART 1000 CCD or SMART APEX II CCD diffractometer
crystallization from
nꢀhexane/CH2Cl2 (1 : 3). Data obtained
ω
-2θ scan mode were collected on a Bruker AXS
complex 1a with the free ligand L2H (0.24 g, 0.94 mmol) and with graphiteꢀmonochromated MoꢀK radiation (
λ = 0.71073 A).
Ru3(CO)12 (0.30 g, 0.47 mmol) as starting materials. Complex The structures were refined on F2 by fullꢀmatrix leastꢀsquares
1b was obtained as orange crystals (0.29 g, 75%). Anal. Calc. methods using the SHELXTLꢀ97 program package. All nonꢀ
for C20H13BrNO10Ru3: C, 29.64; H, 1.62; N, 1.73. Found (%): hydrogen atoms were refined anisotropically and hydrogen
1
C, 29.51; H, 1.49; N, 1.84. H NMR (500 MHz, CDCl3, 298 atoms were introduced into calculated positions with the
K):δ 7.57ꢀ7.51 (m, 2H, Pyꢀ
H), 7.23 (d,
J
= 7.3 Hz, 1H, Pyꢀ
H), displacement factors of the host carbon atoms.
1.99ꢀ1.88(m, 4H, cyclohexylꢀCH2), 1.78ꢀ1.76 (m, 2H,
cyclohexylꢀCH2), 1.55ꢀ1.52 (m, 2H, cyclohexylꢀCH2), 1.33ꢀ
1.25 (m, 2H, cyclohexylꢀCH2) ppm. 13C NMR (125 MHz,
CDCl3, 298 K):δ 206.0, 204.3, 202.8, 199.3, 197.2, 196.6,
193.0, 189.5, 185.7, 170.7, 147.2, 138.8, 128.6, 118.8, 91.3,
43.8, 38.5, 25.4, 21.6, 20.7 ppm. IR(υCO, KBr, cmꢀ1): 1919 (s),
2023 (s), 2055 (s), 2096 (s).
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
Complex 1c. Complex 1c was synthesized following analogous
methods as described above for the synthesis of complex 1a
with the free ligand
This work was financially supported by the Hebei Natural
Science Foundation of China (No. B2015205116,
B2016205051 and B2017205006), the Education Department
Foundation of Hebei Province (No. ZD2018005) and Science
Foundation of Hebei Normal University (Nos. L2017Z02 and
L2018B08).
L
3H (0.20 g, 0.94 mmol) and Ru3(CO)12
(0.30 g, 0.47 mmol) as starting materials. Complex 1c was
obtained as orange crystals (0.30 g, 82%). Anal. Calc. for
C17H9BrNO10Ru3: C, 26.50; H, 1.18; N, 1.82. Found (%): C,
1
26.39; H, 1.32; N, 1.68; H NMR (500 MHz, CDCl3, 298 K):δ
7.58 (d,
7.18 (d,
C
J
J
= 7.0 Hz, 1H, Pyꢀ
= 6.7 Hz, 1H, Pyꢀ
H
H
), 7.54 (t,
), 1.71 (s, 3H, CH3), 1.58 (s, 3H,
J
= 7.7 Hz, 1H, Pyꢀ
H
),
Notes and references
H3) ppm. 13C NMR (125 MHz, CDCl3, 298 K):δ 206.6, 203.8,
1
2
3
(a) G.-J. Brink, I. W. C. E. Arends and R. A. Sheldon, Science,
2000, 287, 1636-1639; (b) M. Vazylyev, D. Sloboda-Rozner, A.
Haimov, G. Maayan and R. Neumann, Top.Catal., 2005, 34
93-99; (c) O. Das and T. K. Paine, Green Chem., 2014, 40-69.
(a) T. Mallat and A. Baiker, Chem. Rev., 2004, 104, 3037-
3058; (b) N. Gunasekaran, N. Remya, S. Radhakrishnan and R.
Karvembu, J. Coord. Chem., 2011, 64, 491-501; (c) C.
Parmeggiani and F. Cardona, Green Chem., 2012, 14, 547-564.
(a) Q. X. Kang, J. J. Luo, Y. B. Bai, Z. W. Yang and Z. Q. Lei, J.
Organomet. Chem., 2005, 690, 6309-6313; (b) A. Sarbajna, I.
Dutta, P. Daw, S. Dinda, S. M. W. Rahaman and A. Sarkarand
203.0, 199.3, 196.7, 193.0, 189.9, 185.4, 170.1, 147.0, 138.9,
128.7, 118.8, 89.3, 34.3, 32.0 ppm. IR (υCO, KBr, cmꢀ1): 2095
(s), 2055 (s), 2026 (s), 2013 (s), 2001 (s), 1989 (s), 1965 (s),
1925 (s).
Complex 1d. Complex 1d was synthesized following
analogous methods as described above for the synthesis of
complex 1a with the free ligand L4H (0.26 g, 0.94 mmol) and
Ru3(CO)12 (0.30 g, 0.47 mmol) as starting materials. Complex
1d was obtained as orange crystals (0.31 g, 78%). Anal. Calc.
for C22H11BrNO10Ru3: C, 31.74; H, 1.33; N, 1.68. Found (%):
C, 31.82; H, 1.46; N,1.52. 1H NMR (500 MHz, CDCl3, 298
,
and J. K. Bera, ACS Catal. 2017, 7, 2786−2790; (c) R. Antony,
R. Marimuthu, P. Vishnoi and R. Murugavel, Inorg. Chim.
Acta, 2018, 469, 173-182.
K):δ 7.89 (t,
J
= 7.7 Hz, 1H, Pyꢀ
=5 Hz, 1H, Arꢀ
= 6.3 Hz, 2H, Arꢀ
H
H
), 7.51 (d,
), 7.21ꢀ7.24 (m, 3H, Arꢀ
), 2.00 (s, 3H, CH3) ppm.
J = 7.8 Hz, 1 H,
4
5
(a) G. Zhang, X. Han, Y. Luan, Y. Wang, X. Wen and C. Ding,
Chem. Commun., 2013, 49, 7908-7910.; (b) T. J. Brown, M.
Cumbes, L. J. Diorazio, G. J. Clarkson and M. Wills, J. Org.
Chem., 2017, 82, 10489-10503; (c) W. C. Ho, K. Chung, A. J.
Ingram and R. M. Waymouth, J. Am. Chem. Soc., 2018, 140
748-757.
(a) J. E. Steves and S. S. Stahl, J. Am. Chem. Soc., 2013, 135
Pyꢀ
Pyꢀ
H
H
), 7.39 (t,
), 6.87 (d,
J
J
H,
H
13C NMR (125 MHz, CDCl3, 298 K):δ 206.5, 206.0, 204.2,
196.2, 194.5, 191.0, 165.1, 152.8, 148.1, 137.5, 128.1, 128.0,
126.0, 124.2, 123.6, 93.5, 32.1 ppm. IR(υCO, KBr, cmꢀ1): 2093
(s), 2057 (s), 1964 (s), 1929 (s).
,
,
15742-15745; (b) W. Schilling, D. Riemer, Y. Zhang, N. Hatami
and S. Das, ACS Catal., 2018, , 5425-5430; (c) Y. Matsukawa,
T. Hirashita and S. Araki, Eur. J. Org. Chem., 2018, 11, 1359-
1363.
8
Procedure for dehydrgenative oxidation of secondary
alcohols. A mixture of an alcohol substrate (1.0 mmol),
complex 1c (0.02 mmol) and DBU (0.4 mmol) in 2.0 mL of
toluene was heated to refluxing temperature for 10 h under N2
atmosphere. After required reaction period, the mixture was
cooled to room temperature and the formed H2 was vented off.
The reaction products were analyzed by GC. Pure ketone
derivatives were isolated by column chromatography using
6
7
(a) J. R. Holum, J. Org. Chem., 1961, 26, 4814–4816; (b) G.
Tojo and M. Ferna´ndez, Springer, New York, 2010.
(a) R. J. Highet and W. C. Wildman, J. Am. Chem. Soc., 1955,
77, 4399–4401; (b) A. J. Fatiadi, J. Chem. Soc. B, 1971, 889–
894.
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