5552 Inorganic Chemistry, Vol. 48, No. 12, 2009
Otero et al.
0
0
0
0
0
0
Me3,3 ), 2.32 (s, 3 H, Me5), 2.36 (s, 3 H, Me5 ), 0.77 [s, 9 H,
C(CH3)3], 4.91 [m, JHH = 6.3 Hz, 3 H, OCH(CH3)2], 1.17
[d, JHH = 6.3 Hz, 18 H, OCH(CH3)2]. 13C{1H} NMR
(CDCl3, 297 K):0δ 64.6 (CH), 88.3 (CHa), 150.3, 150.0, 137.04,
(C3,3 or 5,5 ), 106.2 (C4), 106.4 (C4 ), 14.7, 14.6 (Me3,3 ), 11.3
0
(Me5), 11.4 (Me5 ), 119.0 (Cd), 32.2 (Ce), 38.1 (Cg), 41.9 (Cf), 40.4
(Cb), 123.2 (Cc), 31.7 (Ch), 21.3 (Meg), 26.8 (Meg), 74.8 [OCH
(CH3)2], 25.3 [OCH(CH3)2], 26.0 [OCH(CH3)2]. IR (Nujol mull,
cm-1): 1573 ν(CdN), 682 ν(Ti-O).
0
0
136.0 (C3,3 or 5,5 ), 106.1 (C4), 106.6 (C4 ), 14.5, 14.6 (Me3,3 ),
0
11.2 (Me5), 11.5 (Me5 ), 35.7 [C(CH3)3], 26.0 [C(CH3)3], 74.9
[OCH(CH3)2], 26.2 [OCH(CH3)2]. IR (Nujol mull, cm-1): 1576
ν(CdN), 687 ν(Ti-O).
Synthesis of [Zr(OiPr)3(R,R-bpzmm)] (18). The synthetic
procedure was the same as that for complex 12, using Zr(OiPr)4
(0.22 g, 0.56 mmol) and 6 (0.20 g, 0.56 mmol), to give 18 as
a white solid. Yield: 70% (0.24 g, 0.39 mmol). [R]D25: +18.67
(c 1.00, CH2Cl2). Anal. Calcd for C30H50N4O4Zr: C, 57.95; H,
8.05; N, 9.01. Found: C, 58.07; H, 8.44; N, 9.20. 1H NMR
(CDCl3, 297 K): δ 5.96 (s, 1 H, CH), 4.75 (s, 1 H, CHa), 5.86 (s, 1
Synthesis of [Ti(OtBu)3(bpzb)] (14). The synthetic proce-
dure was the same as that for complex 12, using Ti(OtBu)4
(0.50 g, 1.47 mmol) and 3 (0.43 g, 1.47 mmol), to give 14 as a
white solid. Yield: 74% (0.61 g, 1.10 mmol). Anal. Calcd for
C28H52N4O4Ti: C, 60.44; H, 9.35; N, 10.07. Found: C, 60.12;
0
0
H, H4), 5.83 (s, 1 H, H4 ), 2.51 (s, 3 H,0 Me3), 2.31 (s, 3 H, Me3 ),
2.37 (s, 3 H, Me5), 2.28 (s, 3 H, Me5 ), 5.49 (s, 1 H, Hd), 2.20
(m, 2 H, He), 2.08, 0.76 (m, 2 H, geminal-Hh), 1.96 (m, 1 H, Hf),
1.87 (m, 1 H, Hb), 1.19 (s, 3 H, Meg), 0.73 (s, 3 H, Meg), 4.43
[m, JHH = 6.3 Hz, 3 H, OCH(CH3)2], 1.21 [d, JHH = 5.86 Hz,
9 H, OCH(CH3)2], 1.24 [d, JHH = 5.37 Hz, 9 H, OCH(CH3)2].
13C{1H} NMR (CDCl3,0 297 K): δ 70.2 (CH), 80.9 (CHa), 150.09,
H, 9.01; N, 9.76. 1H NMR (CDCl3, 297 K): δ 6.22 (s, 1 H, CH),
0
3.88 (s, 1 H, CHa), 5.77 (s, 1 H, H4), 5.78 (s, 1 H, H4 ), 2.37 (s, 3 H,
0
0
Me3), 2.54 (s, 3 H, Me3 ), 2.20 (s, 3 H, Me5), 2.37 (s, 3 H, Me5 ),
0.85 [s, 9 H, C(CH3)3], 1.30 [s, 27 H, OC(CH3)3]. 13C{1H} NMR
(CDCl3, 297 K): δ 64.7 (CH), 88.1 (CHa), 150.4, 149.8, 137.4,
0
0
0
136.4 (C3,3
5,5 ), 106.3 (C4), 105.4 (C4 ), 14.5 (Me3),
or
0
0
0
0
14.8 (Me3 ), 10.3 (Me5), 11.3 (Me5 ), 35.2 [C(CH3)3], 25.8
[C(CH3)3], 34.1 [OC(CH3)3], 27.3 [OC(CH3)3]. IR (Nujol mull,
cm-1): 1573 ν(CdN), 685 ν(Ti-O).
150.6, 138.9, 137.9 (C3,3 or 5,5 ), 106.2 (C4,4 ), 14.4, 14.3 (Me3,3 ),
0
11.7 (Me5), 11.5 (Me5 ), 118.9 (Cd), 32.0 (Ce), 38.1 (Cg), 41.6
(Cb), 40.4 (Cf), 123.2 (Cc), 31.6 (Ch), 21.3 (Meg), 26.3 (Meg), 74.2
[OCH(CH3)2], 27.69, 27.48, 27.46, 27.40, 27.24, 27.21 [OCH-
(CH3)2]. IR (Nujol mull, cm-1): 1571 ν(CdN), 661 ν(Zr-O).
Synthesis of [TiCl(NMe2)2(bpzb)] (19). To an orange
solution of 7 (0.50 g, 1.07 mmol) in dry THF (70 mL) was added
a solution of Me3SiCl in THF (0.13 mL, 1.07 mmol). The
reaction mixture was stirred for 1 h. The solvent was removed
under vacuum, and the resulting solid was extracted with
hexane. The solvent was removed to give a red solid. Yield:
65% (0.32 g, 0.69 mmol). Anal. Calcd for C20H37ClN6OTi: C,
52.13; H, 8.04; N, 18.24. Found: C, 51.93; H, 8.15; N, 18.06. 1H
NMR (CDCl3, 297 K): δ 5.98 (s, 1 H, CH), 4.12 (s, 1 H, CHa),
Synthesis of [Ti(OiPr)3(bpzte)] (15). The synthetic pro-
cedure was the same as that for complex 12, using Ti(OiPr)4
(0.50 g, 1.71 mmol) and 4 (0.55 g, 1.71 mmol), to give 15 as a
white solid. Yield: 78% (0.72 g, 1.32 mmol). Anal. Calcd for
C28H44N4O4Ti: C, 61.32; H, 8.03; N, 10.22. Found: C, 61.25;
H, 7.69; N, 9.87. 1H NMR (CDCl3, 297 K): δ 5.94 (s, 1 H, CH),
0
5.44 (s, 1 H, CHa), 5.65 (s, 1 H, H4), 5.89 (s, 1 H, H4 ), 2.58 (s, 3 H,
0
0
Me3), 2.59 (s, 3 H, Me3 ), 2.29 (s, 3 H, Me5), 2.35 (s, 3 H, Me5 ),
7.01-6.95 (m, 4 H, Ph-Me), 1.59 (s, 3 H, Ph-Me), 5.01 [m, JHH
6.3 Hz, 3 H, OCH(CH3)2], 1.22 [d, JHH = 6.3 Hz, 18 H, OCH
=
(CH3)2]. 13C{1H} NMR (CDCl3, 297 K): δ0 70.2 (CH),
0
82.4 (CHa0 ), 150.6, 150.2, 137.2, 137.1 (C3,3 or 5,5 ), 105.5 (C40),
5.29 (s, 1 H, H4), 5.33 (s, 1 H, H4’), 3.67 (s, 6 H, NMe2), 3.85
0
0
106.6 (C4 ), 14.2 (Me3), 14.7, (Me3 ), 11.2 (Me5), 11.4 (Me5 ),
140.9-126.1 (Ph-Me), 21.3 (Ph-Me), 75.3 [OCH(CH3)2], 26.2
[OCH(CH3)2]. IR (Nujol mull, cm-1): 1571 ν(CdN), 685 ν(Ti-O).
Synthesis of [Ti(OEt)3(R,R-bpzmm)] (16). The synthetic
procedure was the same as that for complex 12, using Ti(OEt)4
(0.12 mL, 0.57 mmol) and 6 (0.20 g, 0.57 mmol), to give 16 as
a white solid. Yield: 85% (0.26 g, 0.48 mmol). [R]D25: +28.64
(c 1.00, CH2Cl2). Anal. Calcd for C27H44N4O4Ti: C, 60.46; H,
(s, 6 H, NMe2), 2.45 (s, 3 H, Me3), 2.44 (s, 3 H, Me3 ), 1.69 (s, 3 H,
0
Me5), 1.62 (s, 3 H, Me5 ), 0.75 [s, 9 H, C(CH3)3]. 13C{1H} NMR
(CDCl3, 297 K): δ 64.3 (CH), 89.1 (CHa), 151.8, 149.9, 137.01,
0
0
0
135.8 (C3,3 or 5,5 ), 106.4, 105.8 (C4,4 ), 14.1 (Me3), 14.2 (Me3 ),
0
10.7 (Me5), 10.4 (Me5 ), 25.6 [C(CH3)3], 30.0 [C(CH3)3],
50.8, 49.6 (NMe2). IR (Nujol mull, cm-1): 1575 ν(CdN), 325
ν(Ti-Cl).
Synthesis of [TiCl(NMe2)2(R,R-bpzmm)] (20). The syn-
thetic procedure was the same as that for complex 19, using 11
(1.02 g, 1.91 mmol) and Me3SiCl in THF (0.24 mL, 1.91 mmol),
to give 20 as a white solid. Yield: 70% (0.70 g, 1.34 mmol).
[R]D25: +23.74 (c 1.00, CH2Cl2). Anal. Calcd for C25H41ClN6O-
Ti: C, 57.22; H, 7.82; N, 16.02. Found: C, 57.07; H, 7.64; N,
16.24. 1H NMR (CDCl3, 297 K): δ 6.08 (s, 1 H, CH), 5.07 (s, 1 H,
CHa), 5.76 (s, 2 H, H4), 2.57 (s, 3 H, Me3), 2.17 (s, 3 H, Me 3),
2.30 (s, 3 H, Me5), 2.23 (s, 3 H, Me5), 5.51 (s, 1 H, Hd), 2.19
(m, 2 H, He), 2.10, 0.90 (m, 2 H, geminal-Hh), 1.98 (m, 1 H, Hf),
1.56 (m, 1 H, Hb), 1.08 (s, 3 H, Meg), 0.75 (s, 3 H, Meg), 3.44
(s, 6 H, NMe2), 3.28 (s, 6 H, NMe2). 13C{1H} NMR (CDCl3,
297 K): δ 68.8 (CH), 86.3 (CHa), 152.1, 145.6, 139.7, 138.6
1
8.21; N, 10.45. Found: C, 60.67; H, 8.34; N, 10.76. H NMR
(CDCl3, 297 K): δ 6.11 (s, 10 H, CH), 5.25 (s, 1 H, CHa), 5.80
(s, 1 0H, H4), 5.73 (s, 1 H,0 H4 ), 2.19 (s, 3 H, Me3), 2.15 (s, 3 H,
Me 3 ), 2.05 (s, 6 H, Me5,5 ), 5.46 (s, 1 H, Hd), 2.14 (m, 2 H, He),
2.37, 0.95 (m, 2 H, geminal-Hh), 2.38 (m, 1 H, Hf), 2.01 (m, 1 H,
Hb), 1.27 (s, 3 H, Meg), 0.77 (s, 3 H, Meg), 4.40 [br s, 6 H,
OCH2CH3], 1.30 [br s, 9 H, OCH2CH3]. 13C{1H} NMR
(CDCl3, 297 K):0δ 74.0 (CH), 75.1 (CHa), 148.1, 147.6, 144.05,
0
0
141.6 (C3,3 or 5,50), 106.8 (C4), 107.3 (C4 ), 13.7, 13.6 (Me3,3 ),
11.3, 11.2 (Me5,5 ), 123.3 (Cd), 31.9 (Ce), 38.0 (Cg), 41.9 (Cf),
40.9 (Cb), 119.8 (Cc), 31.7 (Ch), 26.3 (Meg), 21.3 (Meg), 69.7
[OCH2CH3], 18.9 [OCH2CH3]. IR (Nujol mull, cm-1): 1569
ν(CdN), 687 ν(Ti-O).
0
0
(C3,3 or 5,5 ), 108.1, 107.6 (C4), 15.1, 14.5 (Me3), 11.6, 11.4 (Me5),
123.4 (Cd), 32.4 (Ce), 38.1 (Cg), 41.2 (Cf), 40.9 (Cb), 137.6 (Cc),
31.7 (Ch), 26.2, 21.5 (Meg), 50.7 (NMe2), 49.51 (NMe2). IR
(Nujol mull, cm-1): 1569 ν(CdN), 315 ν(Ti-Cl).
Synthesis of [Ti(OiPr)3(R,R-bpzmm)] (17). The synthetic
procedure was the same as that for complex 12, using Ti(OiPr)4
(0.50 mL, 1.71 mmol) and 6 (0.60 g, 1.71 mmol), to give 17 as
a white solid. Yield: 80% (0.79 g, 1.37 mmol). [R]D25: +21.4
(c 1.00, CH2Cl2). Anal. Calcd for C30H50N4O4Ti: C, 62.29; H,
8.65; N, 9.69. Found: C, 62.07; H, 8.44; N, 9.50. 1H NMR
(CDCl3, 297 K): δ 5.990(s, 1 H, CH), 4.86 (s,01 H, CHa), 5.86 (s, 1
H, H4), 5.84 (s, 10H, H4 ), 2.55 (s, 6 H, Me3,3 ), 2.37 (s, 3 H, Me5),
2.31 (s, 3 H, Me5 ), 5.47 (s, 1 H, Hd), 2.26 (m, 2 H, He), 2.16, 0.90
(m, 2 H, geminal-Hh), 2.01 (m, 1 H, Hf), 1.72 (m, 1 H, Hb), 1.20
(s, 3 H, Meg), 0.83 (s, 3 H, Meg), 4.90 [m, JHH = 6.3 Hz, 3 H,
OCH(CH3)2], 1.20 [d, JHH = 6.3 Hz, 9 H, OCH(CH3)2], 1.24
[d, JHH = 6.3 Hz, 9 H, OCH(CH3)2]. 13C{1H} NMR (CDCl3,
297 K): δ 69.9 (CH), 83.7 (CHa), 151.4, 149.8, 138.7, 136.6
Synthesis of [TiCl2(NMe2)(bpzb)] (21). The synthetic
procedure was the same as that for complex 19, using 7
(0.50 g, 1.07 mmol) and Me3SiCl (0.27 mL, 2.14 mmol), to give
21 as a red solid. Yield: 73% (0.35 g, 0.78 mmol). Anal. Calcd for
C18H31Cl2N5OTi: C, 47.80; H, 6.86; N, 15.49. Found: C, 47.31;
H, 6.70; N, 15.35. 1H NMR (CDCl3, 297 K): δ 5.91 (s, 1 H, CH),
0
3.91 (s, 1 H, CHa), 5.30 (s, 1 H, H4), 5.34 (s, 1 H, H4 ), 3.98 (s, 6 H,
0
NMe2), 2.90 (s, 3 H, Me3), 2.20 (s, 3 H, Me3 ), 1.63 (s, 3 H, Me5),
0
1.64 (s, 3 H, Me5 ), 0.67 [s, 9 H, C(CH3)3]. 13C{1H} NMR
(CDCl3, 297 K): δ 65.1 (CH), 85.6 (CHa), 153.4, 151.5, 137.2,
0
0
0
or
137.1 (C3,3
5,5 ), 108.0 (C4), 106.8 (C4 ), 14.3 (Me3),