Inorganic Chemistry
Article
53.7, 30.2, 5.2. IR (KBr pellets, cm−1): ν, 2965, 1592, 1475, 1437,
1390, 1364, 1257, 1227, 1096, 1026, 804, 757. Anal. Calcd for
C26H48N5Si2Y: C, 54.24; H, 8.40; N, 12.16. Found: C, 54.25; H, 8.19;
N, 12.01.
Full experimental details, characterization data for
compounds 9 and 10, crystallographic data and
refinements for complexes 2a−2h, 4a−4b and 6
Synthesis of 4b. Under an argon atmosphere, an oven-dried
100.0 mL Schlenk flask equipped with a magnetic stir bar was charged
with 3b (0.54 g, 2.00 mmol), [(Me3Si)2N]3Y(μ-Cl)Li(THF)3 (0.83 g,
1.00 mmol), and toluene (13.0 mL) was added at room temperature.
After the reaction mixture was stirred at 90 °C for 12 h, the mixture
was left standing 0.5 h at 90 °C, and the solvent was filtered under
argon. Crystals of 4b were obtained by cooling the solution at room
temperature for several days. Yellow crystals (0.45 g, 57% yield). Mp
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.
1
289−291 °C. H NMR (500 MHz, toluene-d8): δ 8.44−8.43 (m,
2H), 7.09−6.98 (m, 8H), 6.82 (d, J = 7.5 Hz, 2H), 6.64−6.61 (m,
2H), 4.17 (d, J = 6.5 Hz, 4H), 3.57−3.49 (m, 4H), 1.23 (d, J = 7.0
Hz, 24H), 0.09 (s, 16H). 13C NMR (125 MHz, toluene-d8) δ 159.5,
149.4, 144.1, 142.9, 135.9, 124.3, 123.9, 121.9, 57.1, 28.1, 24.4, 2.6. IR
(KBr pellets, cm−1): ν 2962, 1591, 1570, 1459, 1439, 1382, 1362,
1252, 1196, 756. Anal. Calcd for C24H64N5Si2Y: C, 64.34; H, 8.23; N,
8.93. Found: C, 63.41; H, 7.68; N, 8.78.
AUTHOR INFORMATION
Corresponding Authors
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Shuangliu Zhou − Laboratory of Functionalized Molecular
Solids, Ministry of Education, Anhui Laboratory of Molecule-
Based Materials, College of Chemistry and Materials Science,
Anhui Normal University, Wuhu, Anhui 241000, China;
Shaowu Wang − Laboratory of Functionalized Molecular Solids,
Ministry of Education, Anhui Laboratory of Molecule-Based
Materials, College of Chemistry and Materials Science, Anhui
Normal University, Wuhu, Anhui 241000, China; Anhui
Laboratory of Clean Catalytic Engineering, Anhui Laboratory of
Functional Complexes for Materials Chemistry and Application,
College of Biological and Chemical Engineering, Anhui
Polytechnic University, Wuhu, Anhui 241000, PR China;
Synthesis of 6. Under an argon atmosphere, an oven-dried 100.0
mL Schlenk flask equipped with a magnetic stir bar was charged with
5 (0.44 g, 2.00 mmol), [(Me3Si)2N]3Y(μ-Cl)Li(THF)3 (0.83 g, 1.00
mmol), and toluene (10.0 mL) was added at room temperature. After
the reaction mixture was stirred at 90 °C for 12 h, the solvent was
evaporated under reduced pressure. The resulting solid was extracted
with hexane (2 × 10.0 mL), and the residue was dissolved in hexane/
THF. Crystals of 6 were obtained by cooling the concentrated
solution at room temperature for several days. Colorless crystals (0.34
g, 42% yield). Mp 139−141 °C. 1H NMR (500 MHz, C6D6): δ 7.58−
7.38 (m, 4H), 7.28 (br, 4H), 7.14−7.11 (m, 2H), 4.96−4.94 (m, 2H),
4.57−4.56 (m, 2H), 4.31−3.78 (m, 8H), 3.55−3.53 (m, 4H), 3.29−
2.76 (m, 8H), 2.22−2.18 (m, 4H), 1.78−1.74 (m, 4H), 1.33 (t, J =
6.5 Hz, 4H), 0.49 (s, 18H). 13C NMR (125 MHz, C6D6): δ 144.8,
128.6, 128.4, 126.5, 68.3, 66.4, 63.2, 59.8, 54.7, 54.0, 52.3, 49.7, 25.6,
6.1. IR (KBr pellets, cm−1): ν 2957, 2836, 2686, 1496, 1452, 1348,
1304, 1251, 1116, 1067, 1030, 942, 852, 832, 739, 700, 663, 612.
Anal. Calcd for C36H64ClLiN5O3Si2Y: C, 53.89; H, 8.04; N, 8.73.
Found: C, 53.78; H, 8.16; N, 8.90.
Crystal Structure Determinations. Suitable crystals of com-
plexes 2a−2h, 4a, 4b, and 6 was each mounted in a sealed capillary.
Diffraction was performed on a Burker SMART CCD area detector
diffractometer using graphite-monochromated Mo Kα radiation (λ =
0.71073 Å). An empirical absorption correction was applied using the
SADABS program. All structures were solved by direct methods,
completed by subsequent difference Fourier syntheses, refined
anisotropically for all non-hydrogen atoms by full-matrix least-squares
calculations on F2 using the SHELXTL program package. All
hydrogen atoms were refined using a riding model. See the
collection and refinement information.
Authors
Xiuli Zhang − Laboratory of Functionalized Molecular Solids,
Ministry of Education, Anhui Laboratory of Molecule-Based
Materials, College of Chemistry and Materials Science, Anhui
Normal University, Wuhu, Anhui 241000, China
Xiaofei Fang − Laboratory of Functionalized Molecular Solids,
Ministry of Education, Anhui Laboratory of Molecule-Based
Materials, College of Chemistry and Materials Science, Anhui
Normal University, Wuhu, Anhui 241000, China
Lijun Zhang − Laboratory of Functionalized Molecular Solids,
Ministry of Education, Anhui Laboratory of Molecule-Based
Materials, College of Chemistry and Materials Science, Anhui
Normal University, Wuhu, Anhui 241000, China
Guide Tao − Laboratory of Functionalized Molecular Solids,
Ministry of Education, Anhui Laboratory of Molecule-Based
Materials, College of Chemistry and Materials Science, Anhui
Normal University, Wuhu, Anhui 241000, China
Yun Wei − Laboratory of Functionalized Molecular Solids,
Ministry of Education, Anhui Laboratory of Molecule-Based
Materials, College of Chemistry and Materials Science, Anhui
Normal University, Wuhu, Anhui 241000, China
Xiancui Zhu − Laboratory of Functionalized Molecular Solids,
Ministry of Education, Anhui Laboratory of Molecule-Based
Materials, College of Chemistry and Materials Science, Anhui
Normal University, Wuhu, Anhui 241000, China;
General Procedure for Dehydrogenative Coupling of
Hydrosilanes with Amines. In a glovebox, an oven-dried 25.0
mL open Schlenk flask equipped with a magnetic stir bar was charged
with complex 2a (0.47 mg, 0.01 mol %, dissolved in 10 mL of
toluene). Organosilane Ph2SiH2 (0.92 g, 5.00 mmol) and the
(CH2CH2)2NH (0.36 g, 5.00 mmol) was sequentially added to the
solution. The mixture was reddish black, and the mixture immediately
began to effervesce. The mixture was stirred for 15 min at room
temperature. Volatile solvent was removed under vacuum, the crude
product was purified by vacuum distillation to give product 9aa (1.14
g, 90% yield).
Peng Cui − Laboratory of Functionalized Molecular Solids,
Ministry of Education, Anhui Laboratory of Molecule-Based
Materials, College of Chemistry and Materials Science, Anhui
Normal University, Wuhu, Anhui 241000, China
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Inorg. Chem. XXXX, XXX, XXX−XXX