Huang et al.
t
1
6.89 (m, 3H, Ph), 5.72 (br, 1H, NH), 1.47 (s, 9H, Bu). 13C-NMR
4.65. Found: C, 55.70; H, 6.95; N, 4.55. H-NMR (CDCl3, δ):
7.72-7.51 (m, 4H, Ph), 1.09 (s, 9H, tBuN), -0.91 (s, 6H, AlMe2).
(CDCl3, δ): 159.49 (C)O), 160.96 (d, JC-F ) 5.5 Hz), 158.47 (d,
JC-F ) 5.5 Hz), 130.96 (t, JC-F ) 7.5 Hz), 115.58 (t, JC-F ) 15.8
Hz), 111.73 (d, JC-F ) 19.8 Hz), 111.73 (d, JC-F ) 10.2 Hz) (Ph),
52.42 (C-N), 28.67 (CMe3). IR (KBr, 1500-1700 cm-1): 1645.1
(s), 1590.7 (s), 1549.6 (s). Mass spectrum (EI, m/e): 213 (M+,
52.9%). Mp: 116-117 °C.
13C-NMR (CDCl3, δ): 175.41 (CdN), 138.76, 131.62 (q, JC-F
)
32.8 Hz), 127.34, 125.29 (q, JC-F ) 3.7 Hz, Ph), 123.65 (q, JC-F
) 278.6 Hz, CF3), 52.05 (C-N), 31.25 (CMe3), -8.30 (AlMe2). IR
(KBr, 1500-1700 cm-1): 1642.1 (s), 1549.9 (s), 1508.8 (w). Mp:
110-112 °C.
{Me2Al[η2-tBuNC(Ph-tBu-p)(µ2-O)]}2 (3). To a rapidly stirred
solution of 1 (0.93 g, 4.0 mmol) in hexane (10 mL) was added
Me3Al (2.2 mL, 4.4 mmol). The reaction mixture was refluxed for
24 h, and the volatile materials were removed under vacuum giving
white solids. The residue was extracted with toluene (30 mL), and
the solution was allowed to concentrate to ca. 15 mL. Colorless
crystals were obtained at -20 °C after 16 h. Yield: 0.95 g (82%).
Anal. Calcd for C34H56Al2N2O2: C, 70.56; H, 9.75; N, 4.84.
{Me2Al[η2-tBuNC(p-tBu-Ph)(µ2-O)]AlMe3} (8). This compound
was prepared according to the same procedures described for 3
using 2.2 molar equiv of Me3Al. Colorless crystals were obtained
at 5 °C after 24 h. Yield: 0.85 g (64%). Anal. Calcd for C20H37-
AlNO: C, 66.45; H, 10.32; N, 3.87. Found: C, 66.26; H, 9.43; N,
1
3.36. H-NMR (CDCl3, δ): 7.50-7.29 (m, 4H, Ph), 1.35 (s, 9H,
t
tBuPh), 1.19 (s, 9H, BuN), -0.45 (s, 9H, AlMe3), -1.19 (s, 6H,
AlMe2). 13C-NMR (CDCl3, δ): 173.54 (CdN), 155.23, 127.29,
126.54, 125.22 (Ph), 54.35 (C-N), 35.04 (C-Ph), 31.09 ((CH3)3-
CN), 30.75 ((CH3)3CPh), -8.13 (AlMe3), -10.39 (AlMe2). IR (KBr,
1500-1700 cm-1): 1620.3 (br, s), 1558.1 (m), 1503.5 (m). Mp:
105-106 °C.
1
Found: C, 69.99; H, 9.51; N, 5.32. H-NMR (CDCl3, δ): 7.43-
t
t
7.29 (m, 4H, Ph), 1.34 (s, 9H, BuPh), 1.10 (s, 9H, BuN), -0.88
(s, 6H, AlMe2). 13C-NMR (CDCl3, δ): 168.77 (CdN), 153.20,
130.83, 127.12, 125.01 (Ph), 52.85 (C-N), 34.84 (C-Ph), 31.23
(CMe3), -8.46 (AlMe2). IR (KBr, 1500-1700 cm-1): 1637.0 (s),
1608.9 (s), 1542.2 (s), 1504.9 (s). Mp: 118-120 °C.
{Me2Al[µ,η2-(2,6-iPr,iPr-Ph)NCOPh]}2 (9). To a rapidly stirred
solution of N-(2,6-diisopropylphenyl)benzamide (0.56 g, 2 mmol)
in toluene (10 mL) was added Me3Al (1.2 mL, 2.4 mmol). The
reaction mixture was stirred at 25 °C for 16 h, and the volatile
materials were removed under vacuum giving white solids. The
residue was extracted by toluene (20 mL), and the solution was
allowed to concentrate to ca. 10 mL. Colorless crystals were
obtained at -20 °C after the solution sat overnight. Yield: 0.35 g
(52%). Anal. Calcd for C42H56Al2N2O2: C, 74.75; H, 8.36; N, 4.15.
{Me2Al[η2-tBuNC(Ph-F,F-2,6)(µ2-O)]}2 (4). This compound
was prepared according to the same procedures described for 3
using 2 (0.85 g, 4.0 mmol). Colorless crystals were obtained in
toluene at room temperature after 12 h. Yield: 0.72 g (67%). Anal.
Calcd for C26H36Al2N2O2F4: C, 57.99; H, 6.74; N, 5.20. Found:
C, 58.33; H, 6.68; N, 5.72. 1H-NMR (CDCl3, δ): 7.45-7.39, 7.01-
t
6.95 (m, 3H, Ph), 1.11 (s, 9H, BuN), -0.87 (s, 6H, AlMe2). 13C-
1
NMR (CDCl3, δ): 167.38 (CdN), 160.33 (d, JC-F ) 7.4 Hz),
156.99 (d, JC-F ) 7.4 Hz), 132.02 (t, JC-F ) 10.1 Hz), 113.57 (t,
Found: C, 74.38; H, 8.66; N, 4.29. H-NMR (CDCl3, δ): 7.41-
7.15 (m, 8H, Ph), 3.23 (m, 2H, JH-H ) 6.8 Hz, Me2CH), 1.25,
0.84 (d, 6H, JH-H ) 6.8 Hz, CH3), -0.89 (s, 6H, AlMe2). 13C-
NMR (CDCl3, δ): 173.80 (C-Ph), 143.00, 137.85, 132.80, 131.92,
130.67, 127.83, 127.46, 124.48 (Ph), 28.23 (CMe2), 24.47, 24.05
(CMe2), -10.00 (AlMe2). IR (KBr, 1500-1700 cm-1): 1643.4 (s),
1586.2 (s), 1530.9 (s). Mp: 160-162 °C dec.
{Me2Al[µ,η2-iBuNC(O)Ph]}2 (10). This compound was prepared
according to the same procedures described for 4 using N-
isobutylbenzamide (0.71 g, 4.0 mmol). Colorless crystals were
obtained in toluene at 5 °C after 12 h. Yield: 0.4 g (43%). Anal.
Calcd for C26H40Al2N2O2: C, 66.93; H, 8.64; N, 6.00%. Found:
C, 66.58; H, 9.12; N, 6.64%. 1H-NMR (CDCl3, δ): 7.48-7.39 (m,
JC-F ) 22.8 Hz), 111.63 (d, JC-F ) 23.7 Hz), 111.63 (d, JC-F
)
18.3 Hz, Ph), 53.36 (C-N), 29.96 (CMe3), -9.37 (AlMe2). IR (KBr,
1500-1700 cm-1): 1647.4 (s), 1623.9 (s), 1589.9 (s), 1550.5 (s).
Mp: 168-170 °C.
{Me2Al[η2-tBuNC(Me)(µ2-O)]}2 (5). To a rapidly stirred solu-
tion of N-tert-butylacetamide (0.46 g, 4.0 mmol) in CH2Cl2 (10
mL) was added Me3Al (2.2 mL, 4.4 mmol). The reaction mixture
was stirred for 24 h, and the volatile materials were removed under
a vacuum giving white solids. The residue was extracted with
toluene (30 mL), and the solution was allowed to concentrate to
ca. 15 mL. Colorless crystals were obtained at 5 °C after 72 h.
Yield: 0.41 g (60%). Anal. Calcd for C16H36Al2N2O2: C, 56.12;
5H, Ph), 3.18 (d, 2H, JH-H ) 3.8 Hz, CH2), 1.73 (m, 1H, JH-H
)
1
H, 10.60; N, 8.18. Found: C, 56.22; H, 10.81; N, 7.89. H-NMR
3.4 Hz, Me2CH), 0.68 (d, 6H, JH-H ) 3.4 Hz, CMe2), -1.00 (s,
6H, AlMe2). 13C-NMR (CDCl3, δ): 176.33 (C-Ph), 134.84, 130.33,
128.33, 126.80 (Ph), 56.13 (C-N), 29.53 (CMe2), 19.82 (CMe2),
-10.39 (AlMe2). IR (KBr, 1500-1700 cm-1): 1636.9 (s), 1608.1
(s), 1589.2 (s). Mp: 120-122 °C.
t
(CDCl3, δ): 2.15 (s, 3H, CH3), 1.27 (s, 9H, Bu), -0.79 (s, 6H,
AlMe2). 13C-NMR (CDCl3, δ): 168.09 (CdN), 51.40 (C-N), 30.03
(CMe3), 18.40 (Me), -8.55 (AlMe2). IR (KBr, 1500-1700 cm-1):
1639.4 (s), 1559.5 (m). Mp: 83-85 °C.
{Me2Al[η2-tBuNC(CF3)(µ2-O)]}2 (6). This compound was
prepared according to the same procedures described for 3 using
N-tert-butyltrifluoroacetamide (1.00 g, 6.0 mmol). Colorless crystals
were obtained at -20 °C after 24 h. Yield: 0.75 g (55.6%). Anal.
Calcd for C8H15AlF3NO: C, 42.67; H, 6.71; N, 6.22. Found: C,
{Et2Al[µ,η2-BnNC(O)Ph]}2 (11). To a rapidly stirred solution
of N-benzylbenzamide (0.63 g, 3.0 mmol) in toluene (30 mL) was
added Et3Al (1.6 mL, 3.0 mmol). The reaction mixture was stirred
at room temperature for 6 h and was then concentrated to ca. 10
mL. Colorless crystals were obtained at -20 °C after 48 h. Yield:
0.52 g (59%). Anal. Calcd for C11H13AlF3NO: C, 73.20; H, 7.51;
N, 4.74. Found: C, 73.67; H, 8.05; N, 4.62. 1H-NMR (CDCl3, δ):
1
t
42.75; H, 6.33; N, 6.16. H-NMR (CDCl3, δ): 1.35 (s, 9H, Bu),
-0.71 (s, 6H, Me). 13C-NMR (CDCl3, δ): 149.8 (q, JC-F ) 43.5
Hz), 115.21 (q, JC-F ) 282.7 Hz), 54.76 (N-C), 30.40 (q, JC-F
)
7.43-7.11 (m, 5H, Ph), 4.53 (s, 2H, Ph-CH2), 0.75 (t, 3H, JH-H )
2.3 Hz), -9.78 (Al-CH3). IR (KBr, 1500-1700 cm-1): 1689.4 (s),
1664.5 (s), 1553.1 (m), 1535.2 (m). Mp: 82-84 °C.
8.4 Hz, Me), -0.34 (q, 2H, JH-H ) 8.2 Hz, Al-CH2). 13C-NMR
(CDCl3, δ): 178.06 (C-O), 138.45, 134.23, 130.49, 128.39, 128.35,
127.25, 127.09, 126.94 (Ph), 51.43 (Ph-C-N), 8.09 (CH3), -0.53
(Al-CH2). IR (KBr, 1500-1700 cm-1): 1574.4 (s). Mp: 106-
112 °C.
{Me2Al[η2-tBuNC(Ph-CF3-p)(µ2-O)]}2 (7). This compound was
prepared according to the same procedures described for 3 using
N-tert-butyl-4-trifluoromethylbenzamide (0.49 g, 2.0 mmol) and
Me3Al (1.1 mL, 2.2 mmol). Colorless crystals were obtained in
toluene at 5 °C after the compound sat overnight. Yield: 0.43 g
(71%). Anal. Calcd for C28H38Al2N2O2F6: C, 55.81; H, 6.36; N,
{Me2Al[µ,η2-PhNC(O)CF3]}2 (12). This compound was pre-
pared according to the same procedures described for 11 using 2,2,2-
trifluoro-N-phenylacetamide (1.07 g, 6.0 mmol) and Me3Al (3.0
2992 Inorganic Chemistry, Vol. 41, No. 11, 2002