Inorganic Chemistry
ARTICLE
Synthesis of LAl(OH)[C(Ph)CH(Ph)] (1). To a solution of LAl-
(η2-C2Ph2) (3.1 g, 5.0 mmol) in diethyl ether (100 mL) at À78 °C was
added a solution of water (0.09 mL, 5.0 mmol) in diethyl ether (50 mL).
The orange solution immediately turned to pale yellow. The mixture was
warmed to room temperature and stirred for additional 4 h. The volatiles
were removed under vacuum, and the remaining solid was extracted with
n-hexane (50 mL). It was filtered, the filtrate was concentrated and
stored in a freezer at À40 °C overnight to give white crystals of 1 (2.63 g,
82%). Mp: 166À168 °C. 1H NMR (C6D6, 400 MHz): δ 0.65 (s, 1H,
OH), 1.08 (t, J = 6.4 Hz, 12H, CHMe2), 1.16 (d, J = 6.8 Hz, 6H,
CHMe2), 1.32 (d, J = 6.8 Hz, 6H, CHMe2), 1.59 (s, 6H, β-CMe), 3.39
(sept, 2H, J = 6.80 Hz, CHMe2), 3.75 (sept, 2H, J = 6.80 Hz, CHMe2),
5.00 (s, 1H, γ-CH), 6.31 (d, 2H, J = 7.6 Hz, Ar-H), 6.36 (s, 1H,
CdCHPh), 6.74À6.97 (m, 10H, Ar-H), 7.17À7.27 (m, 6H, Ar-H). 13C
NMR (C6D6, 100 MHz): δ 23.40 (β-Me), 24.36, 24.59, 24.93, 25.29
(CHMe2), 27.85, 29.19 (CHMe2), 98.62 (γ-C), 123.98, 124.32 (Ar),
125.26 (C=CHPh), 126.26, 126.67, 127.42, 127.92, 128.49, 129.63,
139.23, 140.6,2 141.48, 143.57 (Ar), 147.95 (Al-C), 170.27 (NC).
IR(KBr, cmÀ1): 3482 (m, OH). Anal. Calcd for C43H53AlN2O
(640.39): C, 80.59; H, 8.34; N, 4.37. Found: C, 80.53; H, 8.30; N, 4.48.
Synthesis of LAl[C(Ph)CH(Ph)](μÀO)Y(CH2SiMe3)2(THF)2
(2). To a n-hexane solution (60 mL) of Y(CH2SiMe3)3(THF)2 (0.98 g,
2.0 mmol) was added a solution of 1 (1.28 g, 2.0 mmol) in n-hexane
(60 mL) at À78 °C. The mixture was warmed to 0 °C and stirred for
additional 4 h. The solution was concentrated (ca. 20 mL) and stored in
123.43, 127.53 (Ar), 137.12 (5-pyr), 142.07, 149.09 (Ar), 165.12 (2-pyr),
171.60 (NC); the SmÀCH2 13C NMR signal could not be located. Anal.
Calcd for C37H67N2O2Si2Sm (778.47): C, 57.09; H, 8.67; N, 3.60.
Found: C, 56.54; H, 8.70; N, 3.28.
Synthesis of LAl[C(Ph)CH(Ph)](μÀO)Y(CH2SiMe3)[NN](THF)2
(5). To solution (20 mL) of 3 (0.72 g, 1.00 mmol) in toluene was added
a solution of 1 (0.64 g, 1.00 mmol) in toluene (20 mL) at room tem-
perature. After it was stirred for 4 h, volatiles were removed under
vacuum. The remaining solid was dissolved in THF/n-hexane (1:1) and
stored at À40 °C overnight to give 5 as colorless crystals (1.12 g, 86%).
Mp: 138À141 °C. 1H NMR(C6D6, 400 MHz): δ À0.92, À0.88 (dd, 2JHH
=
11.2 Hz, 2JYH = 3.2 Hz, 1H, CH2SiMe3), 0.04, 0.08 (dd, 2JHH = 11.2 Hz,
2JYH = 4.0 Hz, 1H, CH2SiMe3), 0.30 (s, 9H, CH2SiMe3), 0.81 (d, J =
6.4 Hz, 3H, CHMe2), 0.95 (d, J = 6.4 Hz, 3H, CHMe2), 1.01 (d, J = 7.2 Hz,
3H, CHMe2), 1.04 (d, J = 6.4 Hz, 6H, CHMe2), 1.10 (d, J = 6.4 Hz 6H,
CHMe2), 1.14 (d, J = 6.4 Hz, CHMe2), 1.37 (d, J = 6.8 Hz, 3H, CHMe2),
1.39 (br, 8H, THF), 1.46 (d, J = 6.4 Hz, 3H, CHMe2), 1.55 (d, J = 6.8 Hz,
3H, CHMe2), 1.63 (s, 3H, β-Me), 1.64 (d, J = 6.8 Hz, 3H, CHMe2), 1.73
(s, 3H, β-Me), 1.85 (s, 9H, CMe3), 2.96 (m, 1H, CHMe2), 3.07À3.22
(m, 2H, CHMe2), 3.50 (m, 2H, CHMe2), 3.57 (br, 8H, THF), 4.44 (m,
1H, CHMe2), 5.21 (s, 1H, γ-CH), 6.28 (s, 1H, CdCH), 6.42À6.44 (d,
4H, Ar-H), 6.46 (d, J = 3.6 Hz, 2H, pyr-H), 6.62À6.70 (m, 3H, Ar-H),
6.75À6.78 (t, 1H, Ar-H), 6.84À6.89 (m, 3H, Ar-H), 6.91 (d, J = 3.6 Hz,
2H, pyr-H), 6.95À7.03 (m, 3H, Ar-H), 7.07À7.09 (m, 1H, Ar-H),
7.17À7.22 (m, 2H, Ar-H), 7.27À7.35 (m, 2H, Ar-H), 7.65 (s, 1H,
CHdN). 13C NMR (C6D6, 100 MHz): δ 4.49 (SiMe3), 21.94, 22.97
(CHMe2), 23.97, 24.40, 24.57, 24.64 (CHMe2), 24.77, 25.13, 25.24
(CHMe2), 25.70 (THF), 25.82 (CHMe2), 26.76, 26.95 (β-Me), 27.76,
28.02, 28.33, 28.43, 28.47, 28.59, 29.38, 30.82 (CHMe2), 31.43
(YÀCH2SiMe3), 32.38 (CMe3), 34.66 (CMe3), 67.85 (THF), 101.55
(γ-C), 110.51 (pyr), 123.29 (pyr), 123.87, 124.03, 124.27, 124.60, 124.86,
125.69, 125.75 (Ar), 126.16 (CdCHPh), 127.06, 127.27, 128.56,
129.76, 133.80 (Ar), 139.60 (5-pyr), 141.52, 141.69, 142.80, 142.96,
143.14, 144.37, 144.67, 144.86, 145.44, 146.10 (Ar), 149.39 (AlÀC),
162.42 (2-pyr), 165.76 (CHdN), 169.62, 169.99 (NC). Anal. Calcd for
a freezer at À40 °C overnight to give 2 0.5C6H14 as colorless crystals
3
(1.60 g, 76%). Mp: 125 °C (dec.). 1H NMR (C6D6, 400 MHz): δ À0.90
(s, 4H, CH2SiMe3), 0.33 (s, 18H, CH2SiMe3), 1.06 (d, J = 4.2 Hz, 12H,
CHMe2), 1.17 (d, J = 6.4 Hz, 6H, CHMe2), (s, 8H, THF), 1.29 (br, 14H,
THF and β-Me), 1.41 (d, J = 6.4 Hz, 6H, CHMe2), 3.49 (br, 12H, THF
and CHMe2), 4.88 (s, 1H, γ-CH), 6.88À7.59 (m, 16H, Ar-H). 13C
NMR (C6D6, 100 MHz): δ 5.10 (s, SiMe3), 24.11 (CHMe2), 24.56 (d,
J = 6.0 Hz, CH2SiMe3), 25.48 (THF), 26.14, 26.31 (β-Me), 27.77, 28.66
(CHMe2), 69.84 (THF), 100.70 (γ-C), 124.29, 124.69 (Ar), 126.10
(C=CHPh), 126.81, 127.40, 127.81, 130.24, 130.77, 140.47, 140.80,
142.98, 144.90, 145.63 (Ar), 147.70 (Al-C), 170.81 (NC). Anal. Calcd
C76H108AlN4O3SiY 0.5C6H14 (1312.76): C, 72.28; H, 8.83; N, 4.27.
3
for C59H90AlN2O3Si2Y 0.5C6H14 (1090.50): C, 68.29; H, 8.97; N, 2.57.
Found: C, 71.83; H, 8.75; N, 4.18.
3
Found: C, 67.64; H, 8.85; N, 2.38.
Synthesis of LAl[C(Ph)CH(Ph)](μÀO)Sm(CH2SiMe3)[NN]-
(THF) (6). Six was prepared similarly as described for 5 and obtained
as pale-yellow crystals (1.1 g, 85%). Mp: 172 °C (dec). 1H NMR (C6D6,
400 MHz): δ À5.52 (br, m, 1H, CHMe2), À3.33 (br, s, 9H, CMe3),
À2.88 (br, m, 1H, CHMe2), À1.33 (s, 3H, β-Me), À0.45 (s, 3H, CHMe2),
0.27 (s, 3H, CHMe2), 0.67 (br, s, 9H, CH2SiMe3), 0.81 (br, s, 3H,
CHMe2), 0.95 (br, 4H, THF), 1.10 (t, 1H, Ar-H), 1.32 (d, J = 6.4 Hz, 3H,
CHMe2), 1.45 (t, J = 5.2 Hz, 6H, CHMe2), 1.64 (d, J = 6.4 Hz, 3H,
CHMe2), 1.70 (d, J = 6.0 Hz, 3H, CHMe2), 1.92 (s, 3H, β-Me), 2.62 (br,
3H, CHMe2), 2.88 (br, s, 3H, CHMe2), 3.04 (d, J = 4.0 Hz, 3H, CHMe2),
3.35 (br, m, 4H, THF), 4.02 (m, 1H, pyr-H), 4.50 (m, 2H, Ar-H), 4.61
(br, m, 1H, Ar-H), 5.14 (d, J = 6.4 Hz, 1H, γ-H), 6.14 (t, 1H, Ar-H), 6.55
(m, 1H, pyr-H), 6.69 (br, s, 3H, CHMe2), 6.79 (s, 2H, CHMe2), 6.91
(t, 1H, Ar-H), 7.05À7.12 (m, 5H, Ar-H), 7.45À7.61 (m, 7H, Ar-H), 7.70
(s, 2H, CHMe2), 7.81 (m, 1H, Ar-H), 8.28 (s, 1H, CdCHPh), 8.39 (s,
1H, CHdN), 9.45 (br, s, 1H, CH2SiMe3), 10.60 (br, s, 1H, CH2SiMe3).
13C NMR (C6D6, 100 MHz): δ 2.82 (SiMe3), 19.61(CHMe2), 23.78,
24.27, 24.44, 24.62, 24.68 (CHMe2), 24.80, 25.22 (β-Me), 25.41 (THF),
27.40, 28.21, 29.00, 29.19, 29.26 (CHMe2), 30.34(CMe3), 31.17
(CHMe2), 31.55 (CMe3), 68.52 (THF), 101.37 (γ-C), 108.66 (pyr),
121.19 (pyr), 122.98, 123.70, 124.12, 125.05, 125.28, 125.39, 125.97,
126.39 (Ar), 127.39 (CdCHPh), 129.66, 130.46 (Ar), 135.95 (5-pyr),
140.36, 141.00, 143.94, 144.19, 144.52, 144.64, 145.17, 145.25, 146.19,
146.25 (Ar), 148.51(AlÀC), 164.69 (2-pyr), 168.45 (CHdN), 170.23,
170.73 (NC); the SmÀCH2 13C NMR signal could not be located. Anal.
Synthesis of[NN]Y(CH2SiMe3)2(THF)2 (3). To a solution (60 mL)
of Y(CH2SiMe3)3(THF)2 (0.98 g, 2.0 mmol) in n-hexane was added a
solution of [NN]H (0.62 g, 2.0 mmol) in 20 mL of n-hexane at À78 °C.
The mixture was allowed to warm to room temperature and stirred
overnight. It was concentrated to ca. 5 mL, and then THF (3 mL) were
added. The solution was stored at À40 °C overnight to give colorless
crystals of 3 (1.1 g, 75%). Mp: 101À103 °C. 1H NMR (C6D6, 400 MHz):
δ À0.19 (s, 4H, CH2SiMe3), 0.27 (s, 18H, CH2SiMe3), 0.96 (d, J = 6.6 Hz,
6H, CHMe2), 1.14 (d, J = 6.8 Hz, 6H, CHMe2), 1.26 (br, 8H, THF), 1.69
(s, 9H, CMe3), 3.11 (m, 2H, CHMe2), 3.58 (br, s, 8H, THF), 6.40 (d, J =
3.6 Hz, 1H, pyr-H), 6.81 (d, J = 3.6 Hz, 1H, pyr-H), 6.95À7.02 (m, 3H,
Ar-H), 7.51(s, 1H, NdCH). 13CNMR(C6D6, 100 MHz): δ4.46 (SiMe3),
22.65 (CHMe2), 25.42 (THF), 25.97, 28.71 (CHMe2), 32.29 (CMe3),
34.51 (CMe3), 37.47 (d, JYC = 52.3 Hz, YÀCH2), 69.11 (THF), 110.88
(pyr), 123.72 (pyr), 126.01, 126.37 (Ar), 134.27 (5-pyr), 141.91, 148.38
(Ar), 161.94 (2-pyr), 166.14 (NC). Anal. Calcd for C37H67N2O2Si2Y
(717.02): C, 61.98; H, 9.42; N, 3.91. Found: C, 61.51; H, 9.51; N, 3.62.
Synthesis of [NN]Sm(CH2SiMe3)2(THF)2 (4). 4 was prepared
similarly as described for 3 and obtained as orange crystals (0.84 g, 54%).
Mp: 84À86 °C. 1H NMR (C6D6, 400 MHz): δ À4.43 (s, 9H, CMe3),
0.31 (s, 6H, CHMe2), 0.70 (br, 8H, THF), 1.00 (s, 18H, CH2SiMe3),
1.26 (s, 6H, CHMe2), 1.66 (m, 2H, CHMe3), 2.53 (br, 8H, THF), 5.50
(m, 2H, Ar-H), 5.82 (m, 1H, Ar-H), 6.61 (m, 1H, pyr-H), 8.74 (m, 1H,
pyr-H), 9.02 (br, s, 4H, CH2SiMe3). 13C NMR (C6D6, 100 MHz):
δ 3.13 (SiMe3), 21.56 (CHMe2), 24.30, 25.64 (CHMe2), 26.49 (THF),
27.37 (CMe3), 30.18 (CMe3), 67.95 (THF), 109.02 (pyr), 121.63 (pyr),
Calcd for C72H100AlN4O2SiSm 0.5C6H14 (1302.10): C, 69.18; H, 8.28;
3
N, 4.30. Found: C, 68.72; H, 8.35; N, 4.06.
7454
dx.doi.org/10.1021/ic2010584 |Inorg. Chem. 2011, 50, 7453–7459