3740 Organometallics, Vol. 22, No. 18, 2003
Dagorne et al.
2
(C′(4)-Ph), 131.2 (C(3)-PhO), 131.3 (C(5)-PhO), 132.4
(C′(3)-PhO), 134.8 (C′(5)-PhO), 135.5 (C′(6)-PhO), 137.2
(C(1)-Ph), 138.6 (C′(1)-Ph), 146.9 (C′(1)-PhO), 153.4 (C(1)-
PhO). Anal. Calcd for C52H44Al2BF15N2O2: C, 57.89; H, 4.12.
Found: C, 57.51;H, 4.02.
3.20 (m, 6H, H(R)-N and H′(R)-N), 3.12 (d, J HH ) 14 Hz,
1H, PhCH2), 3.34 (d, 2J HH ) 14 Hz, 1H, PhCH′2), 3.41 (d, 2J HH
2
) 14, 1H, PhCH2), 3.50 (m, 1H, H(R)-N), 4.93 (d, J HH ) 14
Hz, 1H, PhCH′2), 6.78 (broad d, 2H, H(3) and H(4)-PhO), 7.16
3
4
(dd, J HH ) 8 Hz, J HH ) 2, H′(3)-PhO), 7.34 (m, 1H, H′(4)-
3
[{2-(CH2NMe2)-6-tBu -C6H3O}2Al2Me3][MeB(C6F 5)3] ([3b/
3b′][MeB(C6F5)3]). In a glovebox, {6-(CH2NMe2)-2-tBu-C6H3O}-
AlMe2 (2b; 150.0 mg, 0.570 mmol) and B(C6F5)3 (81.6 mg, 0.285
mmol) were added to a sample vial and dissolved in 1 mL of
CH2Cl2. The resulting colorless solution was stirred for 15 min
at room temperature and was evaporated to dryness to yield
a colorless foam. Trituration with cold pentane followed by
filtration through a glass frit of the precipitated solid afforded,
after drying under vacuum, a pure 1/1 mixture of [3b][MeB-
(C6F5)3] and [3b′][MeB(C6F5)3] as a colorless solid (190 mg, 81%
yield). Anal. Calcd for C48H52Al2BF15N2O2: C, 55.50; H, 4.82.
PhO), 7.39 (m, 2H, H′(3)- and H(5)-PhO), 7.74 (dd, J HH ) 8
Hz, J HH ) 2 Hz, 1H, H′(5)-Ph). 13C{1H} NMR (100 MHz,
4
CD2Cl2): δ -11.5 (AlMe), -9.72 (AlMe′), -9.71 (AlMe′), 20.2
(C(â)-N), 21.0 (C(â)-N), 21.1 (C′(â)-N), 22.0 (C′(â)-N), 29.3
(C(CH3)3), 32.9 (C(C′H3)3), 34.4 (C(CH3)3), 36.6 (C′(CH3)3), 52.0
(C(R)-N), 55.0 (C′(R)-N), 55.8 (C′(R)-N), 56.8 (C(â)-N), 57.2
(PhC′H2), 58.1 (PhCH2), 119.5 (C(4)-PhO), 120.7 (C(2)-PhO),
127.5 (C′(2)-PhO), 128.1 (C′(4)-PhO), 128.3 (C(3)-PhO),
128.7 (C(5)-PhO), 130.2 (C′(3)-PhO), 134.2 (C′(5)-PhO),
139.5 (C(6)-PhO), 142.3 (C′(6)-PhO), 146.1 (C′(1)-PhO),
154.2 (C(1)-PhO).
1
Da ta for 3c′+ (Min or Isom er , 25%). H NMR (400 MHz,
CD2Cl2): δ -0.97 (s, 3H, AlMe), -0.78 (s, 3H, AlMe′), -0.19
1
Found: C, 55.77; H, 5.07. Complete assignments of the H and
13C NMR resonances of 3b+ and 3b′+ were possible using a
combination of HMQC and HMBC 2D NMR techniques, and
these data are listed below.
t
t
(s, 3H, AlMe′), 1.38 (s, 9H, Bu), 1.47 (s, 9H, Bu′), 1.70-2.20
(m, 7H, H(â)-N and H′(â)-N), 2.25 (m, 1H, H′(â)-N), 2.55-
3.20 (m, 6H, H(R)-N and H′(R)-N), 3.45-3.55 (m, 4H,
Da ta for 3b+. 1H NMR (400 MHz, CD2Cl2): δ -0.71 (s, 3H,
AlMe′), -0.29 (s, 3H, AlMe), -0.09 (s, 3H, AlMe′), 1.45 (s, 9H,
2
2H(R)-N and 1PhCH2), 3.56 (d, J HH ) 14 Hz, 1H, 1PhCH′2),
4.36 (d, 2J HH ) 14 Hz, 1H, PhCH2), 5.53 (d, 2J HH ) 14 Hz, 1H,
t
tBu), 1.52 (s, 9H, Bu′), 2.18 (s, 3H, NMe), 2.19 (s, 3H, NMe′),
PhCH′2), 6.77 (m, 1H, H(4)-PhO), 6.84 (dd, 3J HH ) 8 Hz, 4J HH
2
2.30 (s, 3H, NMe), 2.76 (s, 3H, NMe′), 3.05 (d, J HH ) 14 Hz,
3
4
2
2
) 2 Hz, 1H, H(3)-PhO), 6.98 (dd, J HH ) 8 Hz, J HH ) 2 Hz,
1H, PhCH2), 3.28 (d, J HH )14 Hz, 1H, PhCH′2), 3.64 (d, J HH
3
4
2
1H, H′(3)-PhO), 7.24 (dd, 1H, J HH ) 8 Hz, J HH ) 2 Hz,
) 14, 1H, PhCH2), 4.84 (d, J HH ) 14 Hz, 1H, PhCH′2), 6.82
3
3
H(5)-PhO), 7.39 (m, 1H, H′(4)-PhO), 7.68 (dd, J HH ) 8 Hz,
(broad d, 2H, H(3)- and H(4)-PhO), 7.21 (dd, J HH ) 8 Hz,
4J HH ) 2 Hz, 1H, H′(5)-Ph). 13C{1H} NMR (100 MHz, CD2-
Cl2): δ -12.1 (AlMe), -10.4 (AlMe′), -8.6 (AlMe′), 20.9 (C(â)-
N), 21.1 (C(â)-N), 21.8 (C′(â)-N), 22.6 (C′(â)-N), 29.0 (C(CH3)3),
32.93 (C(C′H3)3), 34.2 (C(CH3)3), 36.5 (C′(CH3)3), 54.6 (C(R)-
N), 55.7 (C′(R)-N), 56.2 (C′(R)-N), 57.4 (C(â)-N), 57.9 (PhC′H2),
59.6 (PhCH2), 119.9 (C(4)-PhO), 121.9 (C(2)-PhO), 126.9
(C′(2)-PhO), 127.6 (C′(4)-PhO), 128.3 (C(3)-PhO), 129.0
(C(5)-PhO), 130.0 (C′(3)-PhO), 134.1 (C′(5)-PhO), 139.4
(C(6)-PhO), 141.7 (C′(6)-PhO), 146.7 (C′(1)-PhO), 155.3
(C(1)-PhO).
4J HH ) 2, H′(3)-PhO), 7.36-7.42 (m, 2H, H(5) and H′(4)-PhO),
7.76 (dd, J HH ) 8 Hz, J HH ) 2 Hz, 1H, H′(5)-Ph). 13C{1H}
NMR (100 MHz, CD2Cl2): δ -12.1 (AlMe), -9.8 (AlMe′), -9.5
(AlMe′), 29.4 (C(CH3)3), 32.9 (C(C′H3)3), 34.4 (C(CH3)3), 36.6
(C′(CH3)3), 44.8 (NMe), 46.8 (NMe′), 47.3 (NMe), 48.1 (NMe′),
62.1 (PhC′H2), 63.1 (PhCH2), 119.8 (C(4)-PhO), 120.33
(C(2)-PhO), 127.3 (C′(2)-PhO), 127.5 (C′(4)-PhO), 128.2
(C(3)-PhO), 129.2 (C(5)-PhO), 131.0 (C′(3)-PhO), 134.5
(C′(5)-PhO), 139.1 (C(6)-PhO), 142.4 (C′(6)-PhO), 146.0
(C′(1)-PhO), 154.0 (C(1)-PhO).
3
4
Da ta for 3b′+. 1H NMR (400 MHz, CD2Cl2): δ -1.00 (s,
3H, AlMe), -0.79 (s, 3H, AlMe′), -0.17 (s, 3H, AlMe′), 1.35 (s,
9H, Bu), 1.51 (s, 9H, Bu′), 2.33 (s, 3H, NMe′), 2.48 (s, 3H,
Da t a for 3d + (Ma jor Isom er , 75%). 1H NMR (400
MHz, CD2Cl2): δ -0.70 (s, 3H, AlMe′), -0.25 (s, 3H, AlMe),
-0.06 (s, 3H, AlMe′), 1.22-1.96 (m, 12H, H(â)-N, H′(â)-N,
t
t
2
t
t
NMe), 2.80 (s, 3H, NMe′), 2.97 (s, 3H, NMe), 3.34 (d, J HH
)
H(γ)-N, and H′(γ)-N), 1.44 (s, 9H, Bu), 1.50 (s, 9H, Bu′),
2.15-2.33 (m, 2H, H(R)-N), 2.45 (broad d, 1H, H′(R)-N),
2
14 Hz, 1H, PhCH2), 3.42 (d, J HH ) 14 Hz, 1H, PhCH′2), 4.68
2
2
2
(d, J HH ) 14 Hz, 1H, PhCH2), 5.53 (d, J HH ) 14 Hz, 1H,
2.61-2.77 (m, 3H, H(R)-N and H′(R)-N), 3.12 (dt, 1H, J HH
3
2
PhCH′2), 6.90 (t, 1H, J HH ) 8 Hz, H(4)-PhO), 7.04 (dd, 1H,
) 13 Hz, J HH ) 4 Hz, H′(R)-N), 3.28 (d, J HH ) 14 Hz, 1H,
3J HH ) 7 Hz, J HH ) 2 Hz, H(3)-PhO), 7.28 (dd, J HH ) 8 Hz,
4
3
2
PhCH2), 3.44 (d, J HH ) 14 Hz, 1H, PhCH′2), 3.56 (broad m,
4J HH ) 2 Hz, 1H, H′(3)-PhO), 7.36-7.42 (m, 2H, H(5)- and
2
2
1H, J HH ) 13 Hz, H′(R)-N), 3.92 (d, J HH ) 14 Hz, 1H,
3
4
2
3
H′(4)-PhO), 7.76 (dd, J HH ) 8 Hz, J HH ) 2 Hz, 1H, H′(5)-
Ph). 13C{1H} NMR (100 MHz, CD2Cl2): δ -13.1 (AlMe), -10.2
(AlMe′), -7.7 (AlMe′), 29.2 (C(CH3)3), 33.0 (C(C′H3)3), 34.2
(C(CH3)3), 36.5 (C′(CH3)3), 46.1 (NMe′), 46.9 (NMe), 48.2 (NMe),
48.4 (NMe′), 61.5 (PhC′H2), 65.0 (PhCH2), 120.32 (C(4)-PhO),
121.6 (C(2)-PhO), 126.8 (C′(2)-PhO), 127.7 (C′(4)-PhO),
128.5 (C(3)-PhO), 128.9 (C(5)-PhO), 130.8 (C′(3)-PhO), 134.2
(C′(5)-PhO), 139.4 (C(6)-PhO), 141.9 (C′(6)-PhO), 146.9
(C′(1)-PhO), 154.7 (C(1)-PhO). Anal. Calcd for C48H52Al2-
BF15N2O2: C, 55.50; H, 4.82. Found: C, 54.77; H, 5.07.
[{2-(CH2NC4H8)-6-tBu -C6H3O}2Al2Me3][MeB(C6F 5)3] ([3c/
3c′][MeB(C6F 5)3]) a n d [{2-(CH2NC5H 10)-6-tBu -C6H 3O}2-
Al2Me3][MeB(C6F 5)3] ([3d /3d ′][MeB(C6F 5)3]). Compounds
[3c/3c′][MeB(C6F5)3] and [3d /3d ′][MeB(C6F5)3] were obtained
by following the same procedure and using the same quantities
as those for [3b/3b′][MeB(C6F5)3] and were obtained in a 3/1
ratio, respectively, in 81% and 75% overall yields. Complete
assignments of the 1H and 13C NMR resonances of 3c+/3c′+
and 3d +/3d ′+ were also possible using a combination of HMQC
and HMBC 2D-NMR techniques, and these data are listed
below.
PhCH2), 4.61 (d, J HH ) 14 Hz, 1H, PhCH′2), 6.82 (t, 1H, J HH
3
) 8 Hz, H(4)-PhO), 6.88 (m, 1H, H(3)-PhO), 7.17 (dd, J HH
4
3
) 8 Hz, J HH ) 2 Hz, H′(3)-PhO), 7.32 (t, 1H, J HH ) 8 Hz,
3
4
H′(4)-PhO), 7.39 (dd, 1H, J HH ) 8 Hz, J HH ) 2 Hz,
3
4
H(5)-PhO), 7.70 (dd, J HH ) 8 Hz, J HH ) 2 Hz, 1H, H′(5)-
Ph). 13C{1H} NMR (100 MHz, CD2Cl2): δ -11.0 (AlMe), -8.7
(AlMe′), -8.51 (AlMe′), 16.7 (C(γ)-N), 16.9 (C′(γ)-N), 21.7
(C′(â)-N), 21.8 (C(â)-N), 21.9 (C′(â)-N), 22.1 (C(â)-N), 29.4
(C(CH3)3), 32.9 (C(C′H3)3), 34.4 (C(CH3)3), 36.5 (C′(CH3)3), 49.9
(C(R)-N), 51.6 (C′(R)-N), 51.7 (C′(R)-N), 53.0 (C(R)-N), 55.2
(PhC′H2), 56.9 (PhCH2), 119.3 (C(2)-PhO), 119.7 (C(4)-PhO),
126.3 (C′(2)-PhO), 127.4 (C′(4)-PhO), 128.3 (C(3)-PhO),
128.9 (C(5)-PhO), 131.0 (C′(3)-PhO), 134.5 (C′(5)-PhO),
139.1 (C(6)-PhO), 142.1 (C′(6)-PhO), 146.5 (C′(1)-PhO),
154.7 (C(1)-PhO).
Da ta for 3d ′+ (Min or Isom er , 25%). H NMR (400 MHz,
CD2Cl2): δ -0.87 (s, 3H, AlMe), -0.77 (s, 3H, AlMe′), -0.16
(s, 3H, AlMe′), 1.22-1.96 (m, 12H, H(â)-N, H′(â)-N,
1
t
t
H(γ)-N, and H′(γ)-N), 1.35 (s, 9H, Bu), 1.37 (s, 9H, Bu′),
2.07-2.48 (m, 3H, H(R)-N and H′(R)-N), 2.55-2.77 (m, 1H,
H(R)-N), 2.80 (m, 1H, H′(R)-N), 2.90 (m, 1H, H(R)-N), 3.06
Da ta for 3c+ (Ma jor Isom er , 75%). 1H NMR (400 MHz,
CD2Cl2): δ -0.69 (s, 3H, AlMe′), -0.33 (s, 3H, AlMe), -0.09
(m, 1H, H′(R)-N), 3.34 (m, 1H, H′(R)-N), 3.77 (d, J HH ) 14
2
2
Hz, 1H, PhCH′2), 4.21 (d, J HH ) 14 Hz, 1H, PhCH2), 4.33 (d,
t
t
(s, 3H, AlMe′), 1.47 (s, 9H, Bu), 1.51 (s, 9H, Bu′), 1.70-2.20
(m, 8H, H(â)-N and H′(â)-N), 2.45 (m, 1H, H′(R)-N), 2.55-
2J HH ) 14 Hz, 1H, PhCH2), 5.30 (d, 2J HH ) 14 Hz, 1H, PhCH′2),
6.87 (t, 1H, 3J HH ) 8 Hz, H(4)-PhO), 6.88 (m, 1H, H(3)-PhO),