Organometallics
Article
OC CH ), 1.42−2.51 (m, 15H, PCH , CH/CH2,Ad), 1.91 (s, 15H,
CH P), 136.2 (C
CH ), 136.3 (C
C,P
CH ), 141.5 (p-
q
3
2
Ph
q,p‑tolyl
3
q,p‑tolyl
3
1
1
C Me ), 3.23−3.25 (m, 1H, PCH ), 5.08−5.09 (m, 1H, C H ), 5.47−
Cq,p‑tolylCH ), 141.8 (d, J = 16.7 Hz, Cq,PhP), 142.1 (d, J
=
5
5
2
5
4
3
C,P
3
1
1
5
.49 (m, 1H, C H ), 5.50−5.52 (m, 1H, C H ), 6.43−6.44 (m, 1H,
18.4 Hz, Cq,PhP), 144.3 (p-Cq,p‑tolylCH ), 146.5 (Cq,ipso) ppm. P{ H}
5
4
5
4
3
C H ), 6.99−7.02 (m, 1H, p-CH P), 7.08−7.11 (m, 1H, p-CH P),
7
ppm. C{ H} NMR (126 MHz, C D , 305 K): δ 12.9 (C Me ), 25.9
NMR (202 MHz, C D , 300 K): δ −20.5 ppm. Anal. Calcd for
5
4
Ph
Ph
6
6
.17−7.20 (m, 4H, 4 × o-CH P), 7.81−7.85 (m, 4H, 4 × m-CH P)
C H ClHfOP: C, 63.60; H, 5.69. Found: C, 63.55; H, 5.61. HR/MS:
Ph
Ph
45 48
13
1
−
calculated m/z 815.2908 [M − Cl ]; measured (ESI) m/z 815.2909.
6
6
5
5
(
CH ), 27.6 (CH ), 27.9 (CH ), 33.6 (CH2,Ad), 33.63 (CHAd),
Synthesis of Ti5a. To a solution of complex Ti4a (0.400 g, 0.556
mmol) in 10 mL of tetrahydrofuran was added a methyllithium
solution (0.4 mL, 0.556 mmol; 1.6 M in diethyl ether). The reaction
mixture was stirred for 16 h at room temperature. The solvent was
completely removed, and the residue was dissolved in 10 mL of
toluene. The solution was filtered, and the residue was washed with
toluene (2 × 8 mL). All volatiles were removed under vacuum to give
complex Ti5a as a pale yellow solid.
Ad
Ad
Ad
3
3
4.7 (CH2,Ad), 35.8 (d, J = 13.4 Hz, OC CH3), 37.3 (CH ), 37.5
C,P q 2,Ad
1
3
(
CH2,Ad), 39.3 (CH2,Ad), 41.2 (d, J = 18.6 Hz, PCH ), 55.3 (d, J
C,P 2 C,P
2
=
2.2 Hz, Cq,exo), 104.3 (C H ), 111.9 (C H ), 112.1 (d, J = 9.2 Hz,
5 4 5 4 C,P
OC ), 112.8 (C H ), 120.1 (C H ), 124.3 (C Me ), 127.4 (p-CH P),
q
5
4
5
4
5
5
Ph
2
2
1
28.2 (d, J = 5.0 Hz, 2 × o-CH P)*, 128.8 (d, J = 7.4 Hz, 2 ×
C,P Ph C,P
2
o-CH P), 129.0 (p-CH P), 133.1 (d, J = 16.8 Hz, 2 × m-CH P),
Ph
Ph
C,P
Ph
2
1
1
35.1 (d, J = 22.8 Hz, 2 × m-CH P), 142.6 (d, J = 19.7 Hz,
C,P Ph C,P
1
Cq,PhP), 142.9 (d, J = 16.9 Hz, C P), 156.4 (Cq,ipso) ppm (asterisk
Data for Ti5a are as follows. Yield: 0.268 g (69%). Mp: 85−87 °C
C,P
q,Ph
3
1
1
indicates overlay with C D signal). P{ H} NMR (202 MHz, C D ,
05 K): δ −22.0 ppm. HR/MS: calculated: m/z 659.2689 [M + H ];
measured (ESI): m/z 659.2682.
̃
dec. IR (ATR): ν 3052, 3019, 2966, 2904, 1510, 1479, 1433, 1375,
6
6
6
6
+
3
1261, 1147, 1120, 1070, 1039, 1024, 943, 911, 866, 841, 813, 797, 733,
−1 1
695, 652, 636, 586, 565 cm . H NMR (500 MHz, C D , 305 K): δ
6 6
Synthesis of Zr2. In a glovebox compound L2 (0.263 g, 1.086
mmol) in n-hexane (3 × 2 mL) was added to a solution of complex
Zr1 (0.500 g, 1.086 mmol) in 12 mL of n-hexane. The suspension was
stirred for 16 h at room temperature. The solid was separated, washed
with n-hexane (3 × 5 mL), and dried under vacuum to give Zr2 as a
pale yellow solid.
Only the clearly assignable signals of the main diastereoisomer are
stated.
Crystals suitable for single-crystal X-ray diffraction were obtained
from a saturated n-hexane solution at −4 °C.
Data for Zr2 are as follows. Yield: 0.630 g (83%). Mp: 102−104 °C.
0.43 (s, 3H, TiCH ), 1.51 (s, 3H, OC CH ), 1.87 (s, 15H, C Me ),
3
q
3
5
5
2
2.14 (s, 3H, CH3,p‑tolyl), 2.17 (s, 3H, CH
), 2.77 (dd, J = 14.6
3,p‑tolyl
H,H
2
2
Hz, J = 6.2 Hz, 1H, CH ), 3.69 (d, J
= 14.6 Hz, 1H, CH2),
P,H
2
H,H
4.84−4.85 (m, 1H, C H ), 5.13−5.17 (m, 2H, 2 × C H ), 6.81−6.83
5
4
5
4
(m, 1H, C H ), 6.92−6.94 (m, 1H, CH
), 6.97−7.05 (m, 7H, 2 ×
5
4
p‑tolyl
o-CH P, 5 × CH
), 7.10−7.13 (m, 2H, 2 × o-CH P) 7.32−7.34
Ph
p‑tolyl
Ph
(m, 1H, CHp‑tolyl), 7.42−7.46 (m, 2H, 2 × m-CH P), 7.49−7.52 (m,
Ph
2H, 2 × m-CH P), 7.55−7.57 (m(br), 2H, 2× CH
), 7.88−7.90
Ph
p‑tolyl
(m, 1H, CH
) ppm. 13C{ H} NMR (126 MHz, C D , 305 K): δ
1
p‑tolyl 6 6
3
12.3 (C
Me ), 21.0 (CH3,p‑tolyl), 21.02 (CH3,p‑tolyl), 33.0 (d, JC,P = 13.8
5
5
1
Hz, OCqCH
), 38.7 (TiCH
(d, JC,P = 2.5 Hz, Cq,exo), 107.8 (d, JC,P = 10.9 Hz, OC
(C ), 109.2 (C ), 109.3 (C ), 119.8 (C2Me ), 120.3 (C
127.8 (p-CHPhP)*, 128.4 (p-CHPhP), 128.5 (d, JC,P = 5.5 Hz, 2 × o-
), 46.5 (d, JC,P = 17.2 Hz, PCH
), 66.6
), 109.1
),
3
3
2
3
2
IR (ATR): ν
̃
2902, 2851, 1705, 1584, 1480, 1450, 1433, 1376, 1277,
q
1
6
217, 1197, 1154, 1092, 1049, 1025, 995, 980, 954, 878, 801, 735, 695,
57, 627, 595, 561 cm . H NMR (500 MHz, C D , 305 K): δ 1.94
5
H
4
5
H
4
5
H
4
5
5
5
H
4
−
1 1
6
6
2
2
(
s, 15H, C Me ), 2.88 (d, J = 16.7 Hz, 1H, PCH ), 3.10−314 (m,
CHPhP), 128.54 (2 × o-CHp‑tolylCH
CHPhP), 128.9 (2 × o-CHp‑tolylCH
3
), 128.6 (d, JC,P = 6.9 Hz, 2 × o-
), 130.3 (2 × m-CHp‑tolylCH ),
), 133.0 (d, JC,P = 18.5 Hz, 2 × m-CHPhP),
3
5
5
H,H
2
1
5
4
1
H, PCH ), 5.35−5.37 (m, 1H, C H ), 5.55−5.57 (m, 1H, C H ),
3
3
2
5
4
5
4
3
.75−5.77 (m, 1H, C H ), 6.27−6.29 (m, 1H, C H ), 7.76−7.81 (m,
131.6 (2 × m-CHp‑tolylCH
133.2 (Cq,p‑tolylCH ), 133.3 (Cq,p‑tolylCH
× m-CHPhP), 136.0 (d, JC,P = 35.1 Hz, Cq,PhP), 136.1 (d, JC,P = 26.5
Hz, Cq,PhP), 142.3 (p-Cq,p‑tolylCH ), 144.1 (p-Cq,p‑tolylCH ), 145.2
(Cq,ipso) ppm (asterisk indicates overlay with C
NMR (202 MHz, C , 305 K): δ −20.2 ppm.
5
4
5
4
13
1
3
H, 4 × m-CH P) ppm. C{ H} NMR (126 MHz, C D , 305 K): δ
3
3
), 134.1 (d, JC,P = 21.0 Hz, 2
Ph
6
6
1
1
1
2.0 (C Me ), 44.2 (d, J = 16.7 Hz, CH ), 55.9 (Cq,exo), 104.8
5
5
C,P
2
2
(
(
C H ), 107.8 (d, JC,P = 9.1 Hz, OC ), 110.31 (C H ), 110.32
3
3
5
4
q
5
4
31
1
31
1
C H ), 115.1 (C H ), 120.9 (C Me ), 154.9 (Cq,ipso) ppm. P{ H}
D signal). P{ H}
6 6
5
4
5
4
5
5
NMR (202 MHz, C D , 305 K): δ −21.5 ppm. Anal. Calcd for
D
6 6
6
6
C H ClOPZr: C, 68.39; H, 6.89. Found: C, 69.68; H, 6.89. HR/MS:
Synthesis of Ti5b. To a solution of complex Ti4b (1.000 g, 1.517
mmol) in 20 mL of tetrahydrofuran was added a methyllithium
solution (1.0 mL, 1.517 mmol; 1.6 M in diethyl ether). The reaction
mixture was stirred for 16 h at room temperature. The solvent was
completely removed, and the residue was dissolved in 15 mL of
toluene. The solution was filtered, and the residue was washed with
toluene (2 × 10 mL). All volatiles were removed under vacuum to give
complex Ti5b as a pale yellow solid.
40
48
+
calculated m/z 701.2257 [M + H ]; measured (ESI) m/z 701.2249.
Synthesis of Hf2. In a glovebox compound L2 (0.199 g, 0.823
mmol) in n-hexane (3 × 3 mL) was added to a solution of complex
Hf1 (0.500 g, 0.823 mmol) in 20 mL of n-hexane. The suspension was
stirred for 16 h at room temperature. The solid was separated, washed
with n-hexane (3 × 8 mL), and dried under vacuum to give Hf2 as a
pale yellow solid.
Crystals suitable for single-crystal X-ray diffraction were obtained
from a saturated n-hexane solution at −4 °C.
Crystals suitable for single-crystal X-ray diffraction were obtained
from a saturated n-hexane solution at −26 °C.
Data for Hf2 are as follows. Yield: 0.505 g (72%). Mp: 91−93 °C
Data for Ti5b are as follows. Yield: 0.880 g (91%). Mp: 170−172
dec. IR (ATR): ν
̃
2955, 2914, 2861, 1510, 1450, 1433, 1377, 1285,
̃
°C dec. IR (ATR): ν 3014, 2990, 2965, 2890, 2848, 1479, 1464, 1450,
1
8
243, 1189, 1174, 1104, 1069, 1038, 1025, 986, 984, 945, 912, 876,
44, 813, 798, 736, 695, 667 cm . H NMR (500 MHz, C D , 300
1432, 1374, 1364, 1233, 1209, 1196, 1165, 1141, 1116, 1091, 1059,
1045, 1026, 982, 952, 912, 878, 847, 814, 754, 745, 732, 696, 657, 631,
−1 1
6
6
−
1 1
K): δ 1.71 (s, 3H, OC CH ), 2.02 (s, 15H, C Me ), 2.09 (s, 3H,
583, 560 cm . H NMR (500 MHz, C
TiCH ), 1.41 (s, 3H, OC CH ), 1.51−1.72 (m, 8H, CHAd/CH2,Ad),
1.85 (s, 15H, C Me ), 2.09−2.12 (m, 2H, CHAd/CH2,Ad), 2.25−2.26
6 6
D , 305 K): δ 0.33 (s, 3H,
q
3
5
5
CH3,p‑tolyl), 2.18 (s, 3H, CH3,p‑tolyl), 2.86−2.90 (m, 1H, PCH ), 3.91−
3
q
3
2
3
.94 (m, 1H, PCH ), 4.97−5.00 (m, 1H, C H ), 5.46−5.47 (m, 1H,
5
5
2
5
4
C H ), 5.69−5.70 (m, 1H, C H ), 6.79−6.80 (m, 1H, C H ), 6.85−
(m, 1H, CHAd/CH2,Ad), 2.36−2.39 (m, 1H, CHAd/CH2,Ad), 2.58−2.59
(m, 1H, CHAd/CH2,Ad), 2.72−2.75 (m, 1H, CHAd/CH2,Ad), 2.78−2.81
5
4
5
4
5
4
6
3
2
.87 (m, 1H, CH ), 6.96−7.07 (m, 8H, 8 × CH ), 7.31−7.38 (m,
Aryl
Aryl
H, 3 × CHAryl), 7.43−7.46 (m, 2H, 2 × m-CH P), 7.56−7.59 (m,
(m, 1H, CH
5.16−5.17 (m, 1H, C
1H, C ), 7.03−7.09 (m, 2H, 2 × p-CHPhP), 7.14−7.19 (m, 4H, 4 ×
o-CHPhP)*, 7.64−7.67 (m, 2H, 2 × m-CHPhP), 7.77−7.80 (m, 2H, 2
2
), 3.13−3.17 (m, 1H, CH
2
), 4.91−4.92 (m, 1H, C
5 4
H ),
), 6.20−6.21 (m,
Ph
13
1
H, 2 × m-CH P), 7.72−7.74 (m, 1H, CH ) ppm. C{ H} NMR
5
H
4
), 5.36−5.36 (m, 1H, C
H
5 4
Ph
Aryl
TS
(
(
126 MHz, C D , 300 K): δ 12.0 (d,
CH3,p‑tolyl), 21.0 (CH3,p‑tolyl), 32.6 (d, J = 12.0 Hz, OC CH ), 42.3
J
= 1.9 Hz, C Me ), 20.9
H
5 4
6
6
C,P
5
5
3
C,P
q
3
1
3
13
1
(
d, J = 17.1 Hz, PCH ), 66.4 (d, J = 2.3 Hz, Cq,exo), 104.9 (d,
× m-CHPhP) ppm. C{ H} NMR (126 MHz, C
(C Me ), 27.8 (CHAd), 28.1 (CHA 3d ), 33.0 (CHAd), 33.9 (CHAd), 34.0
CH2,Ad), 34.8 (CH2,Ad), 35.1 (d, J = 13.1 Hz, OC CH ), 36.3 (d,
D , 305 K): δ 12.2
6 6
C,P
2
C,P
2
JC,P = 10.8 Hz, OC ), 109.2 (C H ), 109.6 (C H ), 110.4 (C H ),
5
5
q
5
4
5
4
5
4
(
1
18.5 (C H ), 120.1 (C Me ), 128.0 (2 × o-CH
CH ), 128.5 (p-
C,P
q
3
5
4
5
5
p‑tolyl
3
2
TS
CH P), 128.54 (p-CH P), 128.6 (d, J = 5.7 Hz, 2 × o-CH P),
J
C,P = 5.1 Hz, TiCH
3
), 37.5 (CH2,Ad), 37.6 (CH2,Ad), 39.6 (CH2,Ad),
42.6 (d, JC,P = 15.9 Hz, PCH ), 55.6 (Cq,exo), 103.1 (C ), 107.9 (d,
), 108.0 (C ), 108.7 (C ), 116.6 (C ),
Ph
Ph
C,P
Ph
2
1
1
1
28.7 (d, J = 6.9 Hz, 2 × o-CH P), 129.1 (2 × o-CHp‑tolylCH3),
30.1 (2 × m-CHp‑tolylCH ), 131.0 (2 × m-CH
2
H
5 4
C,P
Ph
2
CH ), 133.3 (d,
J
C,P = 9.4 Hz, OC
q
5
H
4
H
5
4
H
5 4
3
p‑tolyl
3
3
3
2
JC,P = 18.9 Hz, 2 × m-CH P), 133.9 (d, J = 20.8 Hz, 2 × m-
119.0 (C Me ), 127.8 (p-CH P)*, 128.4 (d, J = 5.8 Hz, 2 × o-
Ph
C,P
5 5 Ph C,P
J
Organometallics XXXX, XXX, XXX−XXX