Organometallics
Article
172.9, 149.9, 140.7, 139.2, 126.8, 123.2, 122.0, 121.3, 119.4, 37.2,
35.5. IR (KBr, cm−1): 3150 (w), 3076 (s), 2955 (s), 2924 (s), 1601
(w), 1577 (m), 1466 (vs), 1442 (s), 1315 (m), 1294 (s), 791 (m),
735 (s), 708 (s), 675 (s). Anal. Calcd for C19H22N6PdS2I: C, 36.12;
H, 3.51; N, 13.30. Found: C, 36.20; H, 3.47; N, 13.25. ESI-MS m/z:
calcd for [C19H22N6PdS2]+ [M − I]+, 503.0305; found, 503.0378.
41.90; H, 4.48; N, 11.33. ESI-MS m/z: calcd for
[C52H66F6N12PPd2S4]+ [M − PF6]+, 1343.2132; found, 1343.2188;
calcd for [C52H66N12Pd2S4]2+ [M − 2PF6]2+, 599.1168; found,
599.1251.
General Procedure for the Reduction of Quinoline
Compounds with Palladium Complex. The palladium complex
(0.001 mmol, 1 mol %), quinoline or a derivative (0.1 mmol), n-
dodecane (0.1 mmol), and ammonia−borane (1 mmol) were added
to toluene (2 mL) in a Schlenk tube and kept at 100 °C to stir for 3 h
under a nitrogen atmosphere. The resulting mixture was filtered
through a small pad of silica using EtOAc and analyzed by GC-MS.
X-ray Structure Determination. Diffraction data of 1b, 2a, and
3b were collected on a Bruker AXS SMART APEX diffractometer,
equipped with a CCD area detector using Cu Kα radiation (λ =
1.54184) for 1b and Mo Kα radiation (λ = 0.71073 Å) for 2a and 3b.
All of the data were collected at 298 K, and the structures were solved
by direct methods and subsequently refined on F2 by using full-matrix
least-squares techniques (SHELXL).67 SADABS68 absorption correc-
tions were applied to the data, all non-hydrogen atoms were refined
anisotropically, and hydrogen atoms were located at calculated
positions. All calculations were performed using the Bruker Smart
program.
1
1b. Yield: 61.0 mg, 92%. H NMR (400 MHz, MeOD-d4): δ 7.75
(d, J = 2.4 Hz, 2H), 7.46 (d, J = 2.4 Hz, 2H), 7.37 (s, 3H), 7.22 (s,
2H), 4.19 (q, J = 7.2 Hz, 4H), 3.18(s, 6H), 1.43 (t, J = 7.2 Hz, 6H).
13C NMR (100 MHz, DMSO-d6): δ 173.2, 149.0, 140.6, 139.1, 126.8,
123.2, 121.4, 120.5, 119.8, 43.5, 37.1, 14.4. IR (KBr, cm−1): 3156 (w),
3116 (m), 3069 (s), 2973 (m), 1614 (w), 1575 (m), 1446 (s), 1352
(m), 1307 (m), 1279 (s), 790 (w), 731 (s), 711 (s). Anal. Calcd for
C21H26N6PdS2I: C, 38.22; H, 3.97; N, 12.73. Found: C, 38.28; H,
3.92; N, 12.65. ESI-MS m/z: calcd for [C21H26N6PdS2]+ [M − I]+,
531.0618; found, 531.0701.
1
2a. Yield: 60.0 mg, 88%. H NMR (400 MHz, DMSO-d6): δ 8.05
(s, 2H), 7.71 (dd, J = 6.0, 2.4 Hz, 2H), 7.69(d, J = 2.4 Hz, 2H), 7.46−
7.41 (m, 5H), 4.01 (s, 6H), 3.70 (s, 6H). 13C NMR (100 MHz,
DMSO-d6): δ 185.5, 149.7, 140.5, 139.2, 134.5, 127.0, 123.3, 122.1,
121.4, 119.5, 111.0, 35.6, 34.5. IR (KBr cm−1): 3173 (w), 3069 (m),
3013 (m), 2922 (s), 1614 (w), 1582 (m), 1471 (vs), 1441 (s), 1380
(s), 1265 (m), 789 (s), 740 (s), 706 (s). Anal. Calcd for
C23H24N6PdS2I: C, 40.51; H, 3.55; N, 12.32. Found: C, 40.56; H,
3.54; N, 12.36. ESI-MS m/z: calcd for [C23H24N6PdS2]− [M − I]+,
553.0463; found, 553.0443.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
■
sı
1
2b. Yield: 64.0 mg, 90%. H NMR (400 MHz, DMSO-d6): δ 8.08
(d, J = 2.0 Hz, 2H), 7.77 (d, J = 2.4 Hz, 2H), 7.72 (dd, J = 6.0, 3.2 Hz,
2H), 7.47−7.40 (m, 5H), 4.13 (q, J = 7.2 Hz, 4H), 4.00 (s, 6H), 1.33
(t, J = 7.2 Hz, 6H). 13C NMR (100 MHz, DMSO-d6): δ 185.8, 148.8,
140.5, 139.0, 134.5, 127.0, 123.3, 121.6, 120.6, 120.0, 111.0, 43.6,
34.4, 14.4. IR (KBr, cm−1): 3153 (w), 3113 (w), 3065 (m), 2976 (m),
2931 (m), 1612 (w), 1580 (w), 1462 (s), 1442 (s), 1346 (m), 1275
(m), 787 (w), 744 (s), 716 (m), 680 (m). Anal. Calcd for
C25H28N6PdS2I: C, 42.29; H, 3.98; N, 11.84. Found: C, 42.33; H,
3.96; N, 11.89. ESI-MS m/z: calcd for [C25H28N6PdS2]+ [M − I]+,
581.0776; found, 581.0755.
General Procedure for the Synthesis of Pd-NHC Complexes
(3a,b). A solution of Pd(SCS)Cl (0.1 mmol), tetramethylbenzobis-
(imidazolium) bromide (0.05 mmol), and Cs2CO3 (98.0 mg, 0.3
mmol) in MeCN (15 mL) was purged with N2 and then stirred at
room temperature for 0.5 h and at 333 K for 18 h. Then the solvent
was removed with a rotary evaporator. The reminding green solid was
washed with H2O (3 × 10 mL) and Et2O (3 × 5 mL), which was then
dried under vacuum pumping to give the intermediate product. The
resulting product was poured into 1/1 MeOH/CH2Cl2 (v/v)
solution, the undissolved precipitate was removed by filtration, excess
aqueous KPF6 (5 mL) was added, and a thick orange precipitate was
obtained by filtration and washed with H2O (3 × 5 mL) and Et2O (3
× 5 mL). The solid was dried under vacuum pumping to give the
corresponding product.
Crystal data and summary of data collection and
refinement, absorption spectra, NMR data, and MS of
palladium complexes (PDF)
Accession Codes
tallographic data for this paper. These data can be obtained
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION
Corresponding Authors
■
Wei-Guo Jia − The Key Laboratory of Functional Molecular
Solids, Ministry of Education, Anhui Laboratory of Molecular-
Based Materials (State Key Laboratory Cultivation Base),
College of Chemistry and Materials Science, Anhui Normal
University, Wuhu 241002, People’s Republic of China; State
Key Laboratory of Structural Chemistry, Fujian Institute of
Research on the Structure of Matter, Chinese Academy of
Science, Fuzhou 350002, People’s Republic of China;
Ying-Feng Han − State Key Laboratory of Structural Chemistry,
Fujian Institute of Research on the Structure of Matter, Chinese
Academy of Science, Fuzhou 350002, People’s Republic of
China; Key Laboratory of Synthetic and Natural Functional
Molecular Chemistry of Ministry of Education, College of
Chemistry and Materials Science, Northwest University, Xi’an
3a. Yield: 36.6 mg, 55%. 1H NMR (400 MHz, DMSO-d6): δ 8.14−
8.06 (m, 6H), 7.70 (s, 4H), 7.45 (s, 6H), 4.11−4.02 (m, 12H), 3.72
(s, 12H). 13C NMR (100 MHz, DMSO-d6): δ 189.2, 150.6, 140.9,
139.8, 132.5, 127.6, 122.7, 122.0, 120.0, 93.6, 36.0, 35.4. IR (KBr
cm−1): 3426 (m), 3163 (vw), 2940 (vw), 1625 (w), 1474 (m), 1389
(m), 1304 (vw), 1231 (w), 1107 (w), 839 (s), 721 (w), 669 (w), 577
(m), 472 (vw). Anal. Calcd for C40H42N12P2F12Pd2S4: C, 36.34; H,
3.20; N, 12.72. Found: C, 36.32; H, 3.26; N, 12.75. ESI-MS m/z:
calcd for [C40H42N12Pd2S4]2+ [M − 2PF6]2+, 515.0227; found,
515.0316.
3b. Yield: 39.4 mg, 53%. 1H NMR (400 MHz, DMSO-d6): δ 8.16−
8.10 (m, 6H), 7.77 (d, J = 2.4, 4H), 7.49−7.42 (m, 6H), 4.14−3.97
(m, 20H), 1.76−1.68 (m, 8H), 1.31−1.21 (m, 8H), 0.85−0.78 (m,
12H). 13C NMR (100 MHz, DMSO-d6): δ 189.2, 149.5, 140.7, 139.5,
132.4, 122.2, 121.7, 120.4, 93.6, 82.6, 48.4, 35.4, 31.2, 19.4, 13.9. IR
(KBr cm−1): 3417 (m), 3148 (w), 2951 (m), 2859 (w), 2176 (w),
1710 (vw), 1618 (vw), 1578 (w), 1461 (s), 1415 (m), 1381 (m),
1250 (w), 1106 (m), 844 (s), 718 (w), 672 (w), 561 (s). Anal. Calcd
for C52H66N12P2F12Pd2S4: C, 41.91; H, 4.46; N, 11.28. Found: C,
Authors
Li-Li Gao − The Key Laboratory of Functional Molecular Solids,
Ministry of Education, Anhui Laboratory of Molecular-Based
Materials (State Key Laboratory Cultivation Base), College of
Chemistry and Materials Science, Anhui Normal University,
Wuhu 241002, People’s Republic of China
F
Organometallics XXXX, XXX, XXX−XXX