Organometallics
Article
with [(Me3Si)2N]3La(μ-Cl)Li(THF)3 (1.77 g, 2.00 mmol), (2,5-
Me2C4H2NCH2CH2)2NH (0.26 g, 1.00 mmol), toluene solution (30
mL), and TMSCN (0.125 mL, 1.00 mmol). The mixture was stirred at
room temperature for 4 h, the solvent was evaporated under reduced
pressure, and the residues were extracted with hexane (15 mL).
Crystals were obtained upon standing the solution at 0 °C for several
days (0.48 g, 53%). mp: 90−92 °C. 1H NMR (500 MHz, toluene-d8):
δ 5.92 (s, 4H, pyr), 3.32−3.30 (m, 4H, CH2), 2.25−2.08 (m, 4H,
CH2), 2.08 (s, 12H, CH3), 0.08 (s, 72H, CH3). 13C NMR (125 MHz,
toluene-d8): δ 129.1, 128.2, 106.4, 50.2, 43.9, 12.7, 2.6. IR (KBr pellets,
cm−1): 3290 (s), 2953 (s), 2816 (m), 2081 (s), 1571 (s), 1517 (m),
1463 (m), 1408 (w), 1301 (w), 1251 (w), 1182 (m), 1126 (s), 1004
(s), 933 (w), 889 (m), 842 (m), 765 (s). Anal. Calcd for
C41H96La2N8Si8: C, 40.91; H, 8.04; N, 9.31. Found: C, 40.77; H,
8.28; N, 9.16.
AUTHOR INFORMATION
Corresponding Author
Notes
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The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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This work was co-supported by the National Natural Science
Foundation of China (Grant Nos. 21432001, 21372010,
21202002, 21372009), the National Basic Research Program
of China (2012CB821604), and grants from Anhui Normal
University.
Preparation of {[η5:η1-(2,5-Me2C4H2NCH2CH2)2N]La[N-
(SiMe3)2](μ-CN)}3 (7). To a 20 mL toluene solution of 2 (0.73 g,
1.01 mmol) was added TMSCN (0.126 mL, 1.01 mmol) at room
temperature. After it was stirred for 4 h, the solvent was removed
under vacuum to give a viscous oil. It was extracted with hexane (15
mL) and was obtained as yellow crystals (0.400 g, 68%). mp: 118−120
°C. 1H NMR (500 MHz, toluene-d8): δ 6.03 (s, 12H, pyr), 3.31−3.30
(m, 12H, CH2), 3.05−3.03 (m, 12H, CH2), 2.20 (s, 36H, CH3), 0.32
(d, 54H, CH3). 13C NMR (75 MHz, THF-d8): δ 129.1, 127.6, 106.1,
51.2, 44.8, 12.8, 2.8. IR (KBr pellets, cm−1): 2945 (m), 2887 (m),
2823 (s), 1517 (s), 1467 (m), 1406 (m), 1365 (s), 1300 (m), 1251
(s), 1182 (s), 1124 (s), 1018 (m), 933 (m), 887 (s), 840 (m). Anal.
Calcd for C69H126N15La3Si6: C, 47.33; H, 7.25; N, 12.00. Found: C,
46.94; H, 7.53; N, 11.75.
REFERENCES
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Preparation of {[η5:η1-(2,5-Me2C4H2NCH2CH2)2N]Nd[N-
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General Experimental Procedure for Cyanosilylation of
Ketones. Under an argon atmosphere, an oven-dried 20.0 mL
Schlenk flask equipped with a magnetic stir bar was charged with the
acetophenone (0.58 mL, 5 mmol) and catalyst 2 (3.4 mg, 0.005
mmol). TMSCN (0.75 mL, 6 mmol) was added, and the resulting
mixture was stirred under solvent-free conditions for 2 h. After
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ASSOCIATED CONTENT
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S
* Supporting Information
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Full experimental details, characterization data for new
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structure determination of complexes 2−8. This material is
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