ꢂꢁꢁꢁ
N. Maudoux et al.: Phenolato-prolinolato Al-In alkyl complexesꢀ
ꢀ139
(0.83 mL of a 0.9 m solution in toluene, 0.75 mmol) in toluene (2 mL). C(CH3)3), 1.53–1.47 (m, 2H, NCH2CH2), 1.33 (s, 9H, C(CH3)3), 1.26–1.22
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The reaction mixture was warmed to room temperature over 30 min (m, 2H, NCHCH2), 0.56 (s, 9H, Si(CH3)3), –ꢀ0.57(d, JHHꢀ=ꢀ12.5 Hz,
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and was then heated at 70°C for 2 h. The volatiles were pumped off 1H, AlCHHSiMe3), –ꢀ0.97 (d, JHHꢀ=ꢀ12.5 Hz, 1H, AlCHHSiMe3) ppm.
and the resulting solid was washed with pentane (2ꢀ×ꢀ2 mL) and dried 13C{1H} NMR (C6D6, 298 K, 125.75 MHz): δꢀ=ꢀ155.8 (Carom-OAl), 149.8 (i-
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under vacuum to afford 1 (365 mg, 92%) as a white powder. H NMR C6H5), 149.7 (i-C6H5), 139.6(Carom-C(CH3)3), 138.8 (Carom-C(CH3)3), 128.6
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(THF-d8, 298 K, 400.16 MHz): δꢀ=ꢀ7.90 (d, JHHꢀ=ꢀ7.4 Hz, 2H, CaromH), (CaromH), 128.5(CaromH), 128.3(CaromH), 126.8(CaromH), 126.4 (CaromH),
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7.62 (d, JHHꢀ=ꢀ7.4 Hz, 2H, CaromH), 7.30–6.99 (m, 7H, CaromH), 6.75 (d, 125.9 (CaromH), 125.8(CaromH), 125.0(CaromH), 123.4 (Carom-CH2N), 79.3
4JHHꢀ=ꢀ2.4 Hz, 1H, CaromH), 4.17 (m, 1H, NCH), 3.88 (d, 2JHHꢀ=ꢀ12.2 Hz, 1H, (CHCO), 75.8 (NCHCO), 60.6 (ArCH2N), 54.9 (NCH2CH2), 35.4 (C(CH3)3),
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Carom-CHHN), 3.13 (m, 1H, NCHHCH2), 2.75 (d, JHHꢀ=ꢀ12.2 Hz, 1H, Carom
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34.3 (C(CH3)3), 32.1 (C(CH3)3), 32.0 (NCH2CH2), 30.3 (C(CH3)3), 20.4
CHHN), 2.46 (m, 1H, NCHHCH2) 1.84 (m, 2H, NCH2CH2), 1.58 (m, 1H, (NCHCH2), 3.1 (Si(CH3)3)) ppm; the resonance for Al-CH2SiMe3 was
NCHCHH), 1.48 (m, 1H, NCHCHH), 1.40 (s, 9H, C(CH3)3), 1.21 (s, 9H, not detected. Elem. Anal. For C36H50AlNO2Si (583.87 g·mol−1): Calcd,
C(CH3)3) ppm. 13C{1H} NMR (THF-d8, 298 K, 100.25 MHz): δꢀ=ꢀ155.9 (Carom
OH), 151.9 (i-C6H5), 150.8 (i-C6H5), 139.2 (Carom-C(CH3)3), 137.3 (Carom
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C, 74.1; H, 8.6; N, 2.4%; Found, C, 73.9; H, 8.5; N, 2.4%.
C(CH3)3), 128.6 (CaromH), 127.9 (CaromH), 126.6 (CaromH), 126.2 (CaromH),
126.1 (CaromH), 126.0 (CaromH), 124.9 (Carom-CH2N), 123.8 (CaromH), 123.7
(CaromH), 77.1 (C(Ph)2), 74.5 (NCH), 62.0 (Carom-CH2N), 56.0 (NCH2CH2),
35.2 (C(CH3)3), 34.4 (C(CH3)3), 31.9 (C(CH3)3), 30.5 (NCHCH2), 30.3
(C(CH3)3), 21.1 (NCH2CH2) ppm. Elem. Anal. For C32H39AlClNO2 (532.09
g.mol−1): Calcd, C, 72.2; H, 7.4; N, 2.6%; Found, C, 72.0; H, 7.5; N, 2.7%.
(S)-{OˆO}GaCl·THF (4·THF):ꢁ(S)-{OˆO}H2 (250 mg, 0.53 mmol) was
dissolved in THF (20 mL) and nBuLi (0.3 mL of a 1.6 m solution in
hexanes) was added dropwise at 0°C. The mixture was stirred at
0°C for 1 h, and it was then added to a suspension of GaCl3 (93 mg,
0.53 mmol) in THF (10 mL). The reaction mixture was stirred over-
night at room temperature, and the volatiles were pumped off. The
resulting colourless solid was dissolved in dichloromethane (10 mL),
(S)-{OˆO}AlMe (2):ꢁ(S)-{OˆO}H2 (500 mg, 1.06 mmol) was dissolved the solution was filtered by cannula to remove insoluble impurities.
in toluene (8 mL) and added dropwise at –ꢀ40°C to a solution of tri- Removal of the solvent under vacuum afforded a colourless pow-
methylaluminium (0.53 mL of a 2.0 m solution in toluene, 1.06 mmol) der. Recrystallisation from a mixture of dichloromethane and pen-
in toluene (2 mL). Then the reaction mixture was warmed to room tane at –ꢀ26°C afforded crystals of 4·THF (0.47 mmol, 89%) suitable
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temperature over 15 min and then stirred at 70°C for 2 h. The vola- for X-ray diffraction crystallography. H NMR (500.13 MHz, 298 K,
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tiles were pumped off and the resulting solid was washed with pen- CD2Cl2): δ 7.90 (d, JHHꢀ=ꢀ7.3 Hz, 2H, CaromH), 7.69 (d, JHHꢀ=ꢀ7.3 Hz, 2H,
tane (3ꢀ×ꢀ3 mL) and dried under vacuum to give 2 (525 mg, 97%) as CaromH), 7.39–7.27 (m, 5H, CaromH), 7.22–7.15 (m, 2H, CaromH), 6.79 (d,
a colourless powder. Crystals suitable for X-ray diffraction crystal- 4JHHꢀ=ꢀ2.5 Hz, 1H, CaromH), 4.39–4.25 (m, 1H, NCHCH2), 4.06 (m, 4H,
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lography were grown from a concentrated toluene solution. 1H NMR OCH2CH2), 3.91 (d, JHHꢀ=ꢀ12.3 Hz, 1H, ArCHHN), 3.35 (m, 1H, NCH-
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(C6D6, 298 K, 400.16 MHz): δꢀ=ꢀ7.88 (d, 3JHHꢀ=ꢀ7.6 Hz, 2H, CaromH), 7.74 (d, HCH2), 2.97 (d, JHHꢀ=ꢀ12.4 Hz, 1H, ArCHHN), 2.91–2.77 (m, 1H, NCH-
3JHHꢀ=ꢀ7.6 Hz, 2H, CaromH), 7.50 (d, 4JHHꢀ=ꢀ2.4 Hz, 1H, CaromH), 7.19–6.99 (m, HCH2), 2.01 (m, 4H, OCH2CH2), 1.94–1.71 (br m, 4H, NCH2CH2 and
5H, CaromH), 6.88 (t, 3JHHꢀ=ꢀ7.3 Hz, 1H, CaromH), 6.69 (d, 4JHHꢀ=ꢀ2.4 Hz, 1H, NCHCH2), 1.43 (s, 9H, (CH3)3), 1.26 (s, 9H, (CH3)3) ppm. 13C{1H} NMR
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CaromH), 4.08 (d, JHHꢀ=ꢀ12.5 Hz, 1H, ArCHHN), 3.68 (m, 1H, NCHCH2), (CD2Cl2, 125.76 MHz, 298 K): δꢀ=ꢀ156.9(Carom-OGa), 149.5(i-C6H5), 139.1,
2.75 (m, 1H, NCHHCH2), 2.42 (d, 2JHHꢀ=ꢀ12.5 Hz, 1H, ArCHHN), 2.00 (m, 128.8, 128.3, 127.2, 126.6, 124.8, 124.5, 123.2 (all arom-C), 78.4 (CHCO),
1H, NCHHCH2), 1.64 (s, 9H, C(CH3)3), 1.58–1.39 (m, 2H, NCH2CH2), 1.34 73.7 (NCHCO), 69.6 (OCH2CH2), 60.7 (ArCH2N), 56.8 (NCH2CH2), 35.3
(s, 9H, C(CH3)3), 1.21–1.04 (m, 2H, NCHCH2), –ꢀ0.44 (s, 3H, Al-CH3) (C(CH3)3), 34.3 (C(CH3)3), 31.7 (C(CH3)3), 30.0 (C(CH3)3), 29.3 (NCH2CH2),
ppm. 13C{1H} NMR (C6D6, 298 K, 100.25 MHz): δꢀ=ꢀ155.8 (Carom-OAl), 26.0 (OCH2CH2), 20.8 (NCHCH2) ppm. Elem. Anal. For C36H47ClGaNO3
149.9 (i-C6H5), 149.7 (i-C6H5), 139.6 (Carom-C(CH3)3), 138.9 (Carom-C(CH3)3), (646.95g·mol−1): Calcd, C, 66.8; H, 7.3; N, 2.2%; Found, C, 66.6; H, 7.3;
128.5 (CaromH), 128.3 (CaromH), 128.2 (CaromH), 127.9 (Carom-CH2N), 126.8 N, 2.1%.
(CaromH), 125.9 (CaromH), 125.8 (CaromH), 125.0 (CaromH), 123.5 (CaromH), 79.3
(CHCO), 75.4 (NCHCO), 60.4 (ArCH2N), 54.8 (NCH2CH2), 35.4 (C(CH3)3),
34.3 (C(CH3)3), 32.1 (NCH2CH2), 32.0 (C(CH3)3), 30.2 (C(CH3)3), 20.4
(NCHCH2) ppm; Al-CH3was not detected. Elem. Anal. for C33H42AlNO2
(511.69 g·mol−1): Calcd, C, 77.5; H, 8.3; N, 2.7%; Found, C, 77.4; H, 8.2;
N, 2.6%.
(S)-{OˆO}Ga(CH2SiMe3) (5):ꢁ(S)-{OˆO}H2(245 mg, 0.52 mmol) and
Ga(CH2SiMe3)3 (172 mg, 0.52 mmol) were dissolved in toluene and
the reaction mixture was stirred at 80°C for 2 h. The volatiles were
removed under vacuum and the resulting solid was washed with
pentane (3ꢀ×ꢀ2 mL). Subsequent drying under vacuum to constant
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weight afforded 5 (283 mg, 87%) as a white powder. H NMR (C6D6,
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(S)-{OˆO}Al(CH2SiMe3) (3):ꢁ(S)-{OˆO}H2(245 mg, 0.52 mmol) and 298 K, 500.13 MHz): δꢀ=ꢀ7.96 (d, JHHꢀ=ꢀ7.7 Hz, 2H, CaromH), 7.80 (d,
Al(CH2SiMe3)3 (150 mg, 0.52 mmol) were dissolved in C6H6 and 3JHHꢀ=ꢀ7.7 Hz, 2H, CaromH), 7.49 (d, 4JHHꢀ=ꢀ2.5 Hz, 1H, CaromH), 7.21–7.05 (m,
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the reaction mixture was stirred at 80°C overnight. The volatiles 4H, CaromH), 6.99 (t, JHHꢀ=ꢀ7.3 Hz, 1H, CaromH), 6.87 (t, JHHꢀ=ꢀ7.3 Hz, 1H,
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were removed under vacuum and the resulting solid was washed CaromH), 6.69 (d, JHHꢀ=ꢀ2.5 Hz, 1H, CaromH), 3.99 (d, JHHꢀ=ꢀ12.0 Hz, 1H,
with pentane (3ꢀ×ꢀ2 mL) and subsequent drying under vacuum ArCHHN), 3.77–3.72 (m, 1H, NCHCH2), 2.90–2.84 (m, 1H, NCHHCH2),
afforded 3 (282 mg, 93%) as a white powder. X-ray quality single- 2.43 (d, 2JHHꢀ=ꢀ12.0 Hz, 1H, ArCHHN), 2.20–2.12 (m, 1H, NCHHCH2), 1.64
crystals were obtained by recrystallisation of the crude prod- (s, 9H, C(CH3)3), 1.54–1.46 (m, 2H, NCH2CH2), 1.35 (s, 9H, C(CH3)3), 1.24–
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uct at 25°C from a concentrated benzene solution. H NMR (C6D6, 1.11 (m, 2H, NCHCH2), 0.46 (s, 9H, Si(CH3)3), –ꢀ0.22(d, 2JHHꢀ=ꢀ12.9 Hz, 1H,
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298 K, 500.13 MHz): δꢀ=ꢀ7.86 (d, JHHꢀ=ꢀ7.3 Hz, 2H, CaromH), 7.75 (d, GaCHHSi), –ꢀ0.69 (d, JHHꢀ=ꢀ12.9 Hz, 1H, GaCHHSi) ppm. 13C{1H} NMR
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3JHHꢀ=ꢀ7.3 Hz, 2H, CaromH), 7.48 (d, JHHꢀ=ꢀ2.6 Hz, 1H, CaromH), 7.08–7.06 (C6D6, 298 K, 125.76 MHz): δꢀ=ꢀ158.5(Carom-OGa), 150.7(i-C6H5), 149.7(i-
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(m, 3H, CaromH), 7.02–6.99 (m, 2H, CaromH), 6.83 (t, JHHꢀ=ꢀ7.3 Hz, 1H, C6H5), 139.4(Carom-C(CH3)3), 138.9(Carom-C(CH3)3), 126.8 (CaromH), 126.3
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CaromH), 6.67 (d, JHHꢀ=ꢀ2.6 Hz, 1H, CaromH), 4.08 (d, JHHꢀ=ꢀ12.5 Hz, 1H, (CaromH), 126.2 (CaromH), 125.9 (CaromH), 124.9 (CaromH), 123.9(Carom-CH2N),
ArCHHN), 3.72 (m, 1H, NCHCH2), 2.83 (m, 1H, NCHHCH2), 2.43 (d, 80.9 (CHCO), 74.8 (NCHCH2), 62.2 (ArCH2N), 56.0 (NCH2CH2), 35.5
2JHHꢀ=ꢀ12.5 Hz, 1H, ArCHHN), 2.04 (m, 1H, NCHHCH2), 1.63 (s, 9H, (C(CH3)3), 34.2 (C(CH3)3), 32.1 (C(CH3)3), 30.4 (C(CH3)3), 29.0(NCH2CH2),
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