Inorganic Chemistry
Article
4H), 7.05 (d, J = 9.1 Hz, 1H) ppm. IR (KBr, disk): υ 3062, 1632, 1562,
1488, 1330, 823, 751, 693 cm−1. Elemental analysis calcd (%) for
C17H13NO: C, 82.57; H, 5.30; N, 5.66. Found: C, 82.63; H, 5.38; N,
5.52.
3.81; N, 2.04. Found: C, 47.18; H, 3.77; N, 2.03. HRMS calcd [M −
Cl]+: m/z 652.0827. Found: 652.0831.
General Procedure for Amide Synthesis from Aldehydes.
The aldehyde (1.0 mmol), NH2OH·HCl (1.0 mmol), NaHCO3 (1.2
mmol), and iridium complex 1 (0.001 mmol) were added to DMSO (2
mL). The mixture was stirred at 50 °C for 6 h. After the reaction, the
solution was extracted with EtOAc, dried over Na2SO4, filtered, and
evaporated to give the crude products, which were further purified by
silica gel column chromatography (CH2Cl2/EA 8:1) to give the
corresponding products.
General Procedure for Amide Synthesis from Nitrile
Hydration. The nitrile (1.0 mmol) and iridium complex 1 (0.005
mmol) were added to H2O (2 mL). The mixture was stirred at 80 °C for
6 h. After the reaction, the solution was extracted with EtOAc and dried
over Na2SO4. The solvent was evaporated under vacuum. The residue
was dissolved in hexane and analyzed by GC-MS.
X-ray Crystallography. Diffraction data of 2 and 3 were collected
on a Bruker Smart APEX CCD diffractometer with graphite-
monochromated Mo Kα radiation (λ = 1.34138 Å). The structures
were solved by direct methods and subsequently refined on F2 using
full-matrix least-squares techniques (SHELXL). SADABS absorption
corrections were applied to the data, all non-hydrogen atoms were
refined anisotropically, and hydrogen atoms were located at the
calculated positions. All calculations were performed using the Bruker
program Smart.
L2, yellow solid, 92% yield. 1H NMR (500 MHz, CDCl3): δ 15.64 (s,
1H), 9.22 (s, 1H), 7.74 (d, J = 9.2 Hz, 1H), 7.67 (d, J = 7.9 Hz, 1H),
7.49 (t, J = 7.5 Hz, 1H), 7.30 (t, J = 7.4 Hz, 1H), 7.23 (d, J = 9.5 Hz,
4H), 7.06 (d, J = 9.2 Hz, 1H), 2.38 (s, 3H) ppm. IR (KBr, disk): υ 3068,
1638, 1561, 1480, 1335, 823, 752, 698 cm−1. Elemental analysis calcd
(%) for C18H15NO: C, 82.73; H, 5.79; N, 5.36. Found: C, 82.77; H,
5.88; N, 5.30.
1
L3, pale yellow solid, 92% yield. H NMR (500 MHz, CDCl3): δ
15.28 (s, 1H), 9.29 (s, 1H), 8.08 (d, J = 8.4 Hz, 1H), 7.80 (d, J = 9.1 Hz,
1H), 7.72 (d, J = 7.9 Hz, 1H), 7.52 (t, J = 7.6 Hz, 1H), 7.41 (d, J = 8.5
Hz, 2H), 7.35 (t, J = 7.4 Hz, 1H), 7.27 (d, J = 2.2 Hz, 1H), 7.10 (d, J =
9.1 Hz, 1H) ppm. IR (KBr, disk): υ 3055, 1643, 1548, 1483, 1336, 815,
742, 706 cm−1. Elemental analysis calcd (%) for C17H12ClNO: C,
72.47; H, 4.29; N, 4.97. Found: C, 72.56; H, 4.35; N, 5.02.
L4, yellow solid, 90% yield. 1H NMR (500 MHz, CDCl3): δ 15.13 (s,
1H), 9.21 (s, 1H), 8.03 (d, J = 8.4 Hz, 1H), 7.76 (d, J = 9.1 Hz, 1H),
7.68 (d, J = 7.9 Hz, 1H), 7.50 (t, J = 7.6 Hz, 1H), 7.44 (s, 1H), 7.39 (d, J
= 7.9 Hz, 1H), 7.33 (t, J = 7.4 Hz, 1H), 7.28 (d, J = 7.9 Hz, 1H), 7.21 (s,
1H), 7.08 (d, J = 9.1 Hz, 1H) ppm. IR (KBr, disk): υ 3059, 1640, 1542,
1477, 1339, 819, 748, 702 cm−1. Elemental analysis calcd (%) for
C17H12BrNO: C, 62.60; H, 3.71; N, 4.29. Found: C, 62.66; H, 3.78; N,
4.33.
Synthesis of Half-Sandwich Iridium Complexes 1−4. A mixture of
[Cp*IrCl2]2 (0.1 mmol), NaOAc (0.4 mmol), and the corresponding
ligand (0.2 mmol) was stirred at 60 °C in 10 mL of methanol for 12 h.
The mixture was filtered and evaporated to give the crude products,
which were further purified by silica gel column chromatography (PE/
EA 2:1) to afford the pure N,O-chelated half-sandwich iridium
complexes 1−4 in moderate yields.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
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sı
1H NMR and 13C NMR spectra of L1−4 and iridium
1, orange solid, 71% yield. 1H NMR (500 MHz, CDCl3): δ 8.87 (s,
1H), 7.77 (d, J = 8.6 Hz, 1H), 7.72 (d, J = 8.2 Hz, 2H), 7.69 (d, J = 9.1
Hz, 1H), 7.60 (d, J = 7.8 Hz, 1H), 7.39 (t, J = 7.7 Hz, 3H), 7.24 (d, J =
6.5 Hz, 3H), 7.14 (t, J = 8.8 Hz, 2H), 1.32 (s, 15H) ppm. 13C NMR
(125 MHz, CDCl3): δ 164.45, 156.61, 154.66, 135.28, 134.39, 128.81,
128.46, 127.26, 127.18, 126.93, 126.26, 125.48, 122.19, 118.82, 110.33,
85.82, 8.53 ppm. IR (KBr, disk): υ 1616, 1549, 1453, 1321, 815, 740,
709 cm−1. Elemental analysis calcd (%) for C27H27ClNOIr: C, 53.23;
H, 4.47; N, 2.30. Found: C, 53.30; H, 4.42; N, 2.31. HRMS calcd [M −
Cl]+: m/z 574.1722. Found: 574.1728.
Accession Codes
graphic data for this paper. These data can be obtained free of
bridge Crystallographic Data Centre, 12 Union Road, Cam-
bridge CB2 1EZ, UK; fax: +44 1223 336033.
2, orange-red solid, 69% yield. 1H NMR (500 MHz, CDCl3): δ 8.87
(s, 1H), 7.78 (d, J = 8.5 Hz, 1H), 7.69 (d, J = 9.2 Hz, 1H), 7.61 (t, J = 7.8
Hz, 3H), 7.39 (t, J = 7.6 Hz, 1H), 7.20 (d, J = 8.0 Hz, 2H), 7.16−7.14
(m, 2H), 2.42 (s, 3H), 1.34 (s, 15H) ppm. 13C NMR (125 MHz,
CDCl3): δ 164.32, 154.43, 154.36, 136.68, 135.04, 134.39, 128.91,
128.77, 127.17, 126.28, 125.23, 122.10, 118.81, 110.34, 85.80, 20.97,
8.55 ppm. IR (KBr, disk): υ 1610, 1536, 1459, 1318, 816, 745, 712
cm−1. Elemental analysis calcd (%) for C28H29ClNOIr: C, 53.96; H,
4.69; N, 2.25. Found: C, 54.03; H, 4.66; N, 2.16. HRMS calcd [M −
Cl]+: m/z 588.1878. Found: 588.1882.
AUTHOR INFORMATION
Corresponding Author
■
Zi-Jian Yao − School of Chemical and Environmental Engineering,
Shanghai Institute of Technology, Shanghai 201418, China; Key
Lab of Synthetic Chemistry of Natural Substances, Shanghai
Institute of Organic Chemistry, Chinese Academy of Sciences,
Fax: +86-21-60873335
3, orange solid, 75% yield. 1H NMR (500 MHz, CDCl3): δ 8.82 (s,
1H), 7.76−7.70 (m, 4H), 7.61 (d, J = 7.8 Hz, 1H), 7.40 (d, J = 7.9 Hz,
3H), 7.18−7.12 (m, 4H), 1.35 (s, 15H) ppm. 13C NMR (125 MHz,
CDCl3): δ 164.78, 155.05, 154.66, 135.63, 134.26, 132.54, 128.87,
128.45, 127.39, 127.21, 126.81, 126.26, 122.38, 118.72, 110.34, 85.88,
8.61 ppm. IR (KBr, disk): υ 1608, 1538, 1463, 1325, 810, 740, 718
cm−1. Elemental analysis calcd (%) for C27H26Cl2NOIr: C, 50.39; H,
4.07; N, 2.18. Found: C, 50.324; H, 4.02; N, 2.26. HRMS calcd [M −
Cl]+: m/z 608.1332. Found: 608.1325.
Authors
Xiao-Nan Fan − School of Chemical and Environmental
Engineering, Shanghai Institute of Technology, Shanghai 201418,
China
Wei Deng − School of Chemical and Environmental Engineering,
Shanghai Institute of Technology, Shanghai 201418, China
Zhen-Jiang Liu − School of Chemical and Environmental
Engineering, Shanghai Institute of Technology, Shanghai 201418,
China
4, orange-red solid, 70% yield. 1H NMR (500 MHz, CDCl3): δ 8.83
(s, 1H), 7.98 (s, 1H), 7.76 (d, J = 8.5 Hz, 1H), 7.71 (d, J = 9.2 Hz, 1H),
7.65−7.59 (m, 2H), 7.40 (d, J = 7.9 Hz, 2H), 7.29 (d, J = 7.9 Hz, 1H),
7.17 (t, J = 7.4 Hz, 1H), 7.11 (d, J = 9.1 Hz, 1H), 1.35 (s, 15H). 13C
NMR (125 MHz, CDCl3): δ 168.44, 156.11, 147.53, 136.69, 133.00,
130.85, 129.41, 129.32, 128.17, 127.47, 123.75, 123.27, 121.41, 119.66,
119.08, 108.99. IR (KBr, disk): υ 1611, 1545, 1460, 1321, 803, 745, 713
cm−1. Elemental analysis calcd (%) for C27H26ClBrNOIr: C, 47.13; H,
Complete contact information is available at:
Notes
The authors declare no competing financial interest.
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Inorg. Chem. XXXX, XXX, XXX−XXX