3
30 cm3 toluene at room temperature. After stirring for 14 h the
solvent was removed under reduced pressure to yield a yellow
solid. This was washed with 10 cm3 cold (Ϫ78 ЊC) pentane and
dried in vacuo (3.04 g, 4.10 × 10Ϫ3 mol, 85%). Crystals suitable
for an X-ray diffraction study were obtained from a saturated
heptane solution.
3H, OCH3), 3.30 (sept, 2H, JH–H = 6.9 Hz, ArCHMe2), 3.14
3
(sept, 2H, JH–H
= 6.1 Hz, N(CHMe2)2), 1.95 (s, 3H,
HC{C(CH3)NAr}), 1.73 (s, 3H, HC{C(CH3)NAr}), 1.36 (d,
6H, 3JH–H = 6.9 Hz, ArCH(CH3)2), 1.17 (d, 6H, 3JH–H = 6.8 Hz,
3
ArCH(CH3)2), 0.82 (d, 12H, JH–H = 6.1 Hz, N(CH(CH3)2)2).
13C NMR (C6D6): δ 168.97 (HC{C(CH3)NAr}2), 163.68
(HC{C(CH3)NAr}2), 149.66 (2-OMeAr Cipso), 145.32 (2,6-iPr2Ar
Cipso), 141.96 (2,6-iPr2Ar Cortho), 138.29 (2-OMeAr C2), 125.31
1H NMR (C6D6): δ 7.22 (m, 4H, 2,6-iPr2Ar Hmeta), 7.12 (m, 2H,
2,6-iPr2Ar Hpara), 6.63–6.55 (m, 4H, 2-OMeAr C4H, C5H), 6.48 (m,
2H, 2-OMeAr C6H), 6.22 (m, 2H, 2-OMeAr C3H), 5.00 (s, br, 2H,
HC{C(CH3)NAr}), 3.29 (sept, br, 4H, CHMe2), 2.83 (s, 6H,
OCH3), 1.84 (s, 6H, HC{C(CH3)NAr}), 1.78 (s, 6H, HC{C-
(CH3)NAr}), 1.27 (d, 12H, 3JH–H = 6.8 Hz, ArCH(CH3)2), 1.24
(br d, 12H, ArCH(CH3)2). 13C NMR (C6D6): δ 165.84 (HC-
{C(CH3)NAr}), 164.93 (HC{C(CH3)NAr}), 151.30 (2-OMeAr
Cipso), 148.95 (2,6-iPr2Ar Cipso), 143.63 (2-OMeAr C2), 140.43
(
2,6-iPr2Ar Cpara), 124.59 (2-OMeAr C4), 123.68 (2,6-iPr2Ar Cmeta),
122.83 (2-OMeAr C6), 122.35 (2-OMeAr C5), 111.28 (2-OMeAr C3),
97.58 (HC{C(CH3)NAr}), 56.27 (OCH3), 48.93 (NCHMe2),
28.18 (ArCHMe2), 25.96 (NCH(CH3)2), 24.29 (HC{C(CH3)-
NAr}), 24.27 (ArCH(CH3)2), 24.09 (ArCH(CH3)2), 22.49
(HC{C(CH3)NAr}). Elemental analysis for C30H45N3OMg: C
73.84, H 9.29, N 8.61%. Found: C 73.61, H 8.97, N 8.41%. IR
(KBr disc)/cmϪ1: 3059w, 2961m, 2867w, 2562w, 1551m, 1527m,
1483m, 1463m, 1405s, 1319m, 1280w, 1262w, 1220w, 1176m,
1118m, 1051m, 1017m, 937w, 795w, 747m, 632w, 566w.
(
2,6-iPr2Ar Cortho), 124.22 (2-OMeAr C4), 123.13 (2,6-iPr2Ar Cmeta, Cpara),
122.59 (2-OMeAr C6), 121.40 (2-OMeAr C5), 111.22 (2-OMeAr C3),
98.57 (HC{C(CH3)NAr}), 55.92 (OCH3), 28.12 (ArCHMe2),
23.81 (ArCH(CH3)2), 23.77 (ArCH(CH3)2), 23.62 (HC{C-
(CH3)NAr}), 23.52 (HC{C(CH3)NAr}). Elemental analysis for
C48H62N4O2Li2: C 77.81, H 8.43, N 7.56%. Found: C 77.71, H
8.58, N 7.47%. IR (NaCl, thin film)/cmϪ1: 3677w, 3054w,
2961m, 2867m, 2837w, 1634s, 1597s, 1564s, 1522m, 1477m,
1463m, 1438m, 1386s, 1363m, 1329w, 1284m, 1241m, 1228m,
1179m, 1119m, 1103w, 1053w, 1032m, 936w, 823w, 789m,
758m, 735m, 701w, 664w.
(BDI-2)ZnNTMS2, 7
A solution of 2 (1.65 g, 4.53 × 10Ϫ3 mol) in 20 cm3 toluene was
added to a stirred solution of Zn[N(SiMe3)2]2 (1.75 g, 4.53 ×
10Ϫ3 mol) in 30 cm3 toluene. The solution was heated to 80 ЊC
for 16 hours. After cooling the solvent was removed under
reduced pressure to yield a white microcrystalline solid (2.59 g,
4.40 × 10Ϫ3 mol, 97%). Crystals suitable for X-ray diffraction
were grown from a saturated solution of heptane at Ϫ10 ЊC.
1H NMR (C6D6): δ 7.14 (m 3H, 2,6-iPr2Ar Hmeta, Hpara), 7.01–
6.96 (m, 2H, 2-OMeAr H), 6.86 (m, 1H, 2-OMeAr H), 6.58 (m, 1H,
2-OMeAr C3H), 4.88 (s, 1H, HC{C(CH3)NAr}), 3.34 (s, 3H,
(BDI-2)MgiPr, 5
iPrMgCl (2.00 cm3, 2.0 M in Et2O, 4.00 × 10Ϫ3 mol) was added
dropwise to a stirred solution of 4 (1.50 g, 2.02 × 10Ϫ3 mol) in
25 cm3 toluene at 0 ЊC. After warming to room temperature
over 14 hours the solvent was removed under reduced pressure
to yield a yellow microcrystalline solid (1.29 g, 2.99 × 10Ϫ3 mol,
75%). Crystals were grown from a heptane solution at Ϫ10 ЊC.
1H NMR (C6D6): δ 7.15 (m, 3H, 2,6-iPr2Ar Hmeta, Hpara) 6.87 (m,
1H, 2-OMeAr C6H), 6.79 (m, 2H, 2-OMeAr C4H, C5H), 6.49 (m,
1H, 2-OMeAr C3H), 4.90 (s, 1H, HC{C(CH3)NAr}), 3.33 (s, 3H,
OCH3), 3.20 (sept, 2H, 3JH–H = 6.9 Hz, ArCHMe2), 1.92 (s, 3H,
HC{C(CH3)NAr}), 1.69 (s, 3H, HC{C(CH3)NAr}), 1.24 (d,
6H, 3JH–H = 6.5 Hz, ArCH(CH3)2), 1.24 (d, 6H, 3JH–H = 7.9 Hz,
MgCH(CH3)2), 1.16 (d, 6H, 3JH–H = 6.8 Hz, ArCH(CH3)2), 0.07
3
OCH3), 3.30 (sept, 2H, JH–H = 6.9 Hz, CHMe2), 1.77 (s, 3H,
HC{C(CH3)NAr}), 1.67 (s, 3H, HC{C(CH3)NAr}), 1.39 (d,
3
3
6H, JH–H = 6.8 Hz, CH(CH3)2), 1.13 (d, 6H, JH–H = 6.8 Hz,
CH(CH3)2), Ϫ0.01 (s, 18H, N(Si(CH3)3)2). 13C NMR (C6D6): δ
168.92 (HC{C(CH3)NAr}), 168.23 (HC{C(CH3)NAr}), 152.72
(
2-OMeAr Cipso), 144.26 (2,6-iPr2Ar Cipso), 142.12 (2,6-iPr2Ar Cortho),
137.48 (2-OMeAr C2), 126.81 (2,6-iPr2Ar Cpara), 126.04 (2-OMeAr C4),
125.92 (2-OMeAr C6), 123.97 (2,6-iPr2Ar Cmeta), 120.61 (2-OMeAr
C5), 111.16 (2-OMeAr C3), 95.81 (HC{C(CH3)NAr}), 54.76
(OCH3),28.13(ArCHMe2),24.53(ArCH(CH3)2),24.71(ArCH-
(CH3)2), 23.86 (HC{C(CH3)NAr}), 22.90 (HC{C(CH3)NAr}),
4.84 (N(Si(CH3)3)2). MS (EI): m/z 587 [M]ϩ, 349 [Mϩ Ϫ CH3],
572 [Mϩ Ϫ Me], 542 [Mϩ Ϫ Me3], 514 [Mϩ Ϫ SiMe3], 427 [Mϩ Ϫ
NSiMe3]. Elemental analysis for C30H49N3OSi2Zn: C 61.15, H
8.38, N 7.13%. Found: C 61.01, H 8.57, N 7.26%. IR (NaCl,
thin film)/cmϪ1: 3620w, 3063w, 2960m, 2860w, 2836w, 1628w,
1555m, 1524m, 1490m, 1441br m, 1403br m, 1321m, 1268m,
1244m, 1215w, 1176w, 1119m, 1049w, 1023m, 996m, 934w,
883m, 801w, 752m, 971w, 628w.
3
(sept, 1H, JH–H = 7.8 Hz, MgCHMe2). 13C NMR (C6D6):
δ
168.97 (HC{C(CH3)NAr}), 164.51 (HC{C(CH3)NAr}),
149.69 (2-OMeAr Cipso), 145.18 (2,6-iPr2Ar Cipso), 141.79 (2,6-iPr2Ar
Cortho), 138.54 (2-OMeAr C2), 125.59 (2,6-iPr2Ar Cpara), 124.68
(
(
2-OMeAr C4), 123.95 (2,6-iPr2Ar Cmeta), 123.30 (2-OMeAr C6), 122.46
2-OMeAr C5), 110.38 (2-OMeAr C3), 97.91 (HC{C(CH3)NAr}),
56.11 (OCH3), 28.51 (ArCHMe2), 25.26 (ArCH(CH3)2), 24.81
(ArCH(CH3)2), 23.95 (MgCH(CH3)2), 23.91 (HC{C(CH3)-
NAr}), 22.82 (HC{C(CH3)NAr}), 9.59 (MgCH(CH3)2). Ele-
mental analysis for C27H38N2OMg: C 75.26, H 8.89, N 6.50%.
Found: C 75.01, H 9.00, N 6.57%. IR (KBr disc): cmϪ1 3062w,
2962m, 2924m, 2868m, 2779m, 2727w, 2688w, 1628w, 1596w,
1553m, 1523m, 1482m, 1459br m, 1399m, 1318br m, 1318m,
1282m, 1262m, 1220m, 1182m, 1115m, 1047m, 1020m, 935w,
863w, 795w, 761m, 748m, 677w, 633w, 578w, 513w, 485w, 435w.
(BDI-2)ZnEt, 8
ZnEt2 (4.99 cm3, 1.1 M in toluene, 5.49 × 10Ϫ3 mol) was added
dropwise to a stirred solution of 2 (2.00 g, 5.49 × 10Ϫ3 mol) in
30 cm3 toluene at 0 ЊC. After stirring for 16 h at room temper-
ature the solvent was removed under reduced pressure to yield a
sticky off-white solid. Trituration with 3 × 15 cm3 heptane at
Ϫ78 ЊC yielded a white microcrystalline solid (2.33 g, 5.09 ×
10Ϫ3 mol, 93%). Crystals suitable for X-ray diffraction were
grown from a saturated heptane solution.
(BDI-2)MgNiPr2, 6
iPr2NH (480 µl, 3.42 × 10Ϫ3 mol) was added dropwise to a
stirred solution of complex 5 (1.45 g, 3.36 × 10Ϫ3 mol) in tolu-
ene (30 cm3) at Ϫ78 ЊC. The reaction was then allowed to warm
to room temperature. After stirring for 14 h the solvent was
removed under vacuum to yield a yellow microcrystalline solid
(1.36 g, 2.79 mmol, 83%). Crystals were grown from a saturated
heptane solution.
1H NMR (C6D6): δ 7.11 (m 3H, 2,6-iPr2Ar Hmeta, Hpara), 6.94 (m,
1H, 2-OMeAr C5H), 6.88 (m, 1H, 2-OMeAr C6H), 6.79 (m, 1H,
2-OMeAr C4H), 6.57 (m, 1H, 2-OMeAr C3H), 5.00 (s, 1H,
HC{C(CH3)NAr}), 3.33 (s, 3H, OCH3), 3.18 (sept, 2H, 3JH–H
=
6.9 Hz, CHMe2), 1.84 (s, 3H, HC{C(CH3)NAr}), 1.69 (s, 3H,
HC{C(CH3)NAr}), 1.20 (d, 6H, JH–H = 6.8 Hz, CH(CH3)2),
1.14 (d, 6H, JH–H = 6.9 Hz, CH(CH3)2), 1.02 (t, 3H, JH–H
8.1 Hz, ZnCH2CH3), 0.29 (q, 2H, 3JH–H = 8.1 Hz, ZnCH2CH3).
13C NMR (C6D6):
167.16 (HC{C(CH3)NAr}), 166.83
(HC{C(CH3)NAr}), 153.64 (2-OMeAr Cipso), 145.55 (2,6-iPr2Ar
3
3
3
=
1H NMR (C6D6): δ 7.15 (s, 3H, 2,6-iPr2Ar Hmeta, Hpara), 6.97 (m,
1H, 2-OMeAr C6H), 6.87–6.82 (m, 2H, 2-OMeAr C4H, C5H), 6.54
(m, 1H, 2-OMeAr C3H), 4.87 (s, 1H, HC{C(CH3)NAr}), 3.39 (s,
δ
D a l t o n T r a n s . , 2 0 0 4 , 5 7 0 – 5 7 8
576