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RSC Advances
Page 5 of 8
DOI: 10.1039/C6RA26537E
Journal Name
ARTICLE
chromatography on silica gel (dichloromethane–methanol, 50 :
1) afforded
MHz, CDCl3): δ 7.47 (d, J = 7.3 Hz, 1H), 7.39 (d, J = 7.6 Hz, 1H), [(Me3Si)2N]3Sm(μ-Cl) Li(THF)3 (1.43 g, 1.6 mmol) and
(η5:η1:η1-L)Sm[N(SiMe3)2] (4b)
.
This compound was
2
(1.75 g, 83% yield) as a yellow solid. 1H NMR (500 prepared following a procedure similar to that for 4a by using
3
(0.50 g,
7.29 (t, J = 7.5 Hz, 1H), 7.22 (t, J = 7.4 Hz, 1H), 6.44 (s, 1H), 6.39 1.8 mmol) in toluene (10.0 mL) as a yellow solid (0.86 g, 90%
(brs, 1H), 3.56 (d, J = 16.1 Hz, 1H), 3.50 (d, J = 16.1 Hz, 1H), yield). The single crystal suitable for X-ray crystallographic
3.46–3.32 (m, 3H), 2.56–2.48 (m, 1H), 2.16–2.06 (m, 1H), 1.97 analysis was obtained by recrystallization from a mixed solvent
(s, 6H), 1.82–1.68 (m, 2H), 1.67–1.58 (m, 1H), 1.34–1.23 (m, of toluene and THF in volume ratio 20 : 1 at –10 °C. 1H NMR
1H), 1.19–1.05 (m, 2H), 1.04–0.92 (m, 1H). 13C NMR (125 MHz, (500 MHz, C6D6): δ 17.90 (s, 1H), 13.31 (d, J = 8.5 Hz, 1H), 10.75
CDCl3): δ 170.5, 144.4, 144.2, 138.6, 131.9, 126.2, 125.0, 123.7, (s, 1H), 6.77 (d, J = 6.8 Hz, 2H), 6.19 (s, 1H), 5.81 (d, J = 7.9 Hz,
119.4, 66.4, 51.4, 39.6, 38.0, 36.9, 32.5, 25.3, 24.6, 21.3. HRMS 1H), 4.09 (t, J = 7.0 Hz, 1H), 3.69 (d, J = 12.1 Hz, 1H), 3.56 (d, J =
(ESI) calcd for C19H27N2O ([M + H]+) calcd for 299.2123, found 13.1 Hz, 1H), 3.25 (s, 1H), 2.92–2.75 (m, 2H), 2.62 (d, J = 14.2
299.2119.
Hz, 1H), 2.49–2.38 (m, 1H), 1.95 (d, J = 12.7 Hz, 1H), 1.23–1.11
Chiral diamine ligand (3). A solution of
2
(0.60 g, 2.0 mmol) (m, 1H), 0.68 (s, 9H), 0.30 (s, 1H), 0.10 (s, 1H), –0.30 (s, 3H), –
in THF (20 mL) was added dropwise to a suspension of LiAlH4 1.65 (s, 1H), –2.69 (s, 3H), –3.24 (s, 9H). 13C NMR (125 MHz,
(0.76 g, 20 mmol) in THF (30 mL) at 0 °C and the resulting C6D6): δ 131.8, 130.5, 120.7, 117.8, 117.2, 116.9, 112.5, 92.6,
mixture was stirred and heated at reflux for 2 days. After being 86.2, 85.3, 82.5, 43.8, 38.4, 32.1, 27.3, 25.6, 23.6, 23.4, 3.5,
quenched with the addition of Na2SO4·10H2O, the suspension 2.2, 1.0. Anal. Calcd for C25H44N3Si2Sm: C, 50.62; H, 7.48; N,
was passed through a pad of Celite, eluting with ether. The 7.08; Found: C, 50.68; H, 7.45; N, 7.02.
solvent was removed under reduced pressure and the residue
was purified by column chromatography on silica gel following
(dichloromethane–methanol, 100 : 1) to give (0.39 g, 69% [(Me3Si)2N]3Lu(μ-Cl)Li(THF)3 (1.46 g, 1.6 mmol) and
(η5:η1:η1-L)Lu[N(SiMe3)2] (4c). This compound was prepared
procedure similar to that for 4a by using
(0.50 g,
a
3
3
yield) as a yellow oil. [α]D20= –66.8 (c = 0.10, CH2Cl2). H NMR 1.8 mmol) as a white solid (0.91 g, 92% yield). The single
(500 MHz, C6D6): δ 7.35 (d, J = 7.5 Hz, 1H), 7.31 (d, J = 7.3 Hz, crystal suitable for X-ray crystallographic analysis was obtained
1H), 7.24 (t, J = 7.4 Hz, 1H), 7.15 (t, J = 7.5 Hz, 1H), 6.10 (s, 1H), by recrystallization from toluene at –10 °C. 1H NMR (500 MHz,
3.18–3.12 (m, 1H), 3.09 (s, 2H), 2.88–2.69 (m, 4H), 2.32–2.21 C6D6): δ 7.76 (d, J = 7.7, 1H), 7.37 (d, J = 8.4 Hz, 1H), 6.95–6.89
(m, 2H), 2.18–2.11 (m, 1H), 2.01 (s, 6H), 1.66–1.52 (m, 3H), (m, 1H), 6.88–6.76 (m, 2H), 6.24 (d, J = 2.6 Hz, 1H), 4.06 (dd, J =
1.23–1.14 (m, 1H), 1.13–1.00 (m, 2H), 0.99–0.87 (m, 1H). 13C 10.7, 7.6 Hz, 1H), 3.83–3.75 (m, 1H), 3.49 (dd, J = 14.1, 6.1 Hz,
NMR (75.5 MHz, CDCl3): δ 144.3, 143.4, 141.4, 127.6, 125.0, 1H), 3.42–3.33 (m, 1H), 2.74–2.63 (m, 1H), 2.26–2.19 (m, 1H),
123.5, 122.7, 117.9, 65.8, 57.6, 44.8, 38.9, 36.8, 30.9, 27.5, 2.15 (td, J = 10.2, 3.6 Hz, 1H), 1.61–1.43 (m, 4H), 1.31–1.21 (m,
24.4, 23.7, 19.6. HRMS (ESI) calcd for C19H29N2 ([M + H]+) calcd 1H), 1.20–1.14 (m, 1H), 1.12–0.77 (m, 6H), 0.60–0.50 (m, 1H),
1
for 285.2331, found 285.2328.
(η5:η1:η1-L)Y[N(SiMe3)2]
(4a)
0.40 (s, 9H), 0.22 (s, 9H). 13C NMR (125 MHz, C6D6): δ 127.4,
.
To
a
solution of 126.9, 123.5, 122.3, 121.9, 121.4, 119.9, 118.9, 92.6, 67.7,
[(Me3Si)2N]3Y(μ-Cl)Li(THF)3 (1.33 g, 1.6 mmol) in toluene (10.0 66.8, 60.8, 43.8, 34.7, 32.2, 29.5, 26.1, 25.3, 20.7, 6.2, 5.1.
mL) was added a solution of (0.50 g, 1.8 mmol) in toluene Anal. Calcd for C25H44N3Si2Lu: C, 48.60; H, 7.18; N, 6.80; Found:
(10.0 mL) at room temperature. The resulting mixture was C, 48.67; H, 7.13; N, 6.74.
3
stirred and heated at 75 °C for 24 h to give a brown solution.
(η5:η1:η1-L)Sc[N(SiMe3)2] (4d). This compound was prepared
Then, the reaction suspension was filtered to remove the LiCl following
a procedure similar to that for 4a by using
precipitate. The filtrate was evaporated under vacuum to [(Me3Si)2N]3Sc(μ-Cl) Li(THF)3 (1.26 g, 1.6 mmol) and (0.50 g, 1.8
remove all volatiles to leave a residue solid, which was washed mmol), except that the reaction mixture was stirred and
with n-hexane (1 mL × 3) and dried under vacuum to afford 4a heated at 90 °C for 36 h. The product 4d was obtained as a
as a grey solid (0.79 g, 93% yield). The single crystal suitable for purple solid (0.73 g, 94% yield). The single crystal suitable for
X-ray
crystallographic
analysis
was
obtained
by X-ray
crystallographic
analysis
was
obtained
by
recrystallization from a mixed solvent of toluene and THF in recrystallization from a mixed solvent of toluene and THF in
volume ratio 20 : 1 at –10 °C. 1H NMR (500 MHz, C6D6): δ 7.76 volume ratio 20 : 1 at –10 °C. 1H NMR (500 MHz, C6D6): δ 7.76–
(dd, J = 8.4, 0.9 Hz, 1H), 7.38 (dt, J = 8.3, 0.9 Hz), 6.95–6.89 (m, 7.69 (m, 1H), 7.37 (d, J = 8.3 Hz, 1H), 6.94–6.88 (m, 1H), 6.87–
1H), 6.87 (d, J = 3.2 Hz, 1H), 6.85–6.81 (m, 1H), 6.30 (d, J = 3.2 6.80 (m, 2H), 6.29 (d, J = 3.2 Hz, 1H), 3.81–3.68 (m, 2H), 3.50–
Hz, 1H), 3.93 (dd, J = 10.5, 7.7 Hz, 1H), 3.83 (td, J = 11.2, 6.0 Hz, 3.42 (m, 1H), 3.42–3.33 (m, 1H), 3.04–2.96 (m, 1H), 2.07–1.98
1H), 3.56 (dd, J = 14.2, 5.8 Hz, 1H), 3.43 (ddd, J = 14.2, 11.5, 7.9 (m, 2H), 1.62 (s, 3H), 1.54–1.46 (m, 2H), 1.23–1.04 (m, 3H),
Hz, 1H), 2.78–2.69 (m, 1H), 2.30–2.21 (m, 1H), 2.12 (td, J = 0.93–0.86 (m, 1H), 0.75 (s, 3H), 0.58–0.48 (m, 1H), 0.41 (s, 9H),
10.1, 3.4 Hz, 1H), 1.59–1.45 (m, 5H), 1.26–1.18 (m, 1H), 1.12– 0.28 (s, 9H). 13C NMR (126 MHz, C6D6): δ 127.0, 126.4, 123.9,
0.94 (m, 3H), 0.92 (s, 3H), 0.60 (qd, J = 12.1, 3.6 Hz, 1H), 0.39 122.2, 122.1, 121.8, 120.9, 120.2, 94.5, 67.0, 60.7, 44.4, 34.1,
(s, 9H), 0.17 (s, 9H). 13C NMR (125 MHz, C6D6): δ 127.4, 127.2, 31.0, 28.8, 25.5, 24.8, 20.2, 6.2, 6.0. Anal. Calcd for
123.5, 122.1, 121.7, 121.2, 120.7, 119.7, 93.3, 68.1, 67.0, 60.8, C25H44N3Si2Sc: C, 61.56; H, 9.09; N, 8.61; Found: C, 61.62; H,
43.5, 35.0, 32.2, 30.0, 26.1, 25.3, 20.7, 6.1, 4.4. Anal. Calcd for 9.03; N, 8.58.
C25H44N3Si2Y: C, 56.47; H, 8.34; N, 7.90; Found: C, 56.53; H, Crystal structure determination
8.30; N, 7.82.
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