A R T I C L E S
Arriola et al.
135.39, 135.90. Peak assignments were performed based on HSQC and
NOESY spectra. HRMS (EI, (M-CH3)+): calcd for C24H30NSiTi
408.1627, found 408.1624. Anal. Calcd for C25H33NSiTi: C, 70.90;
H, 7.85; N, 3.31. Found: C, 70.64; H, 7.91; N, 3.06. The 1H and 13C-
{1H} NMR spectra of this material are shown in the Supporting
Information.
20 °C for approximately 16 h. The mixture was cooled to about -25
°C for about 1 h. The solids were collected on a glass frit by vacuum
filtration and dried under reduced pressure. The dried solid was placed
in a glass fiber thimble, and the solid was extracted continuously with
hexanes using a Soxhlet extractor. After 6 h a dark crystalline solid
was observed in the boiling pot. The mixture was cooled to about -20
°C, and the solid was isolated by filtration from the cold hexanes and
dried under reduced pressure to give 6.65 g of a dark crystalline solid.
The filtrate was discarded. The solids in the extractor were stirred, and
the extraction continued with an additional quantity of mixed hexanes.
After 8 h of extraction, crystals had formed in the boiling hexanes once
again. These were isolated to give an additional 2.05 g of the desired
product as a dark crystalline solid. The combined yield was 8.70 g,
Preparation of Dichloro-[1-[(1,2,3,3a,11b-η)-1H-cyclopenta[l]-
phenanthren-2-yl]-N-(1,1-dimethylethyl)-1,1-dimethylsilanaminato-
(2-)-κN]-titanium (22). To a 250 mL round bottom flask containing
TiCl3(THF)3 (1.17 g, 3.00 mmole) and THF (about 120 mL) was added
at a fast drip rate a THF solution of [2-[[(1,1-dimethylethyl)amino]-
dimethylsilyl]-1H-cyclopenta[l]phenanthren-1-yl]-lithium (21) (1.08 g
in 50 mL). The mixture was stirred at about 20 °C for 1.5 h at which
time solid PbCl2 (0.55 g, 2.0 mmol) was added. After stirring for an
additional 1.5 h, the THF was removed under vacuum and the residue
was extracted with toluene, filtered, and dried under reduced pressure
to give an orange solid. Yield was 1.31 g (93.5%). 1H (CD2Cl4) δ 0.78
(s, 6H, Si(CH3)2), 1.42 (s, 9H, C(CH3)3), 7.09 (s, 2H, H2), 7.65 (m,
1
78%. H (C6D6) δ 0.70 (s, 6H, Si(CH3)2), 1.21 (s, 9H, C(CH3)3), 3.23
(m, H25/H26), 3.76 (m, H24/H27), 6.71 (s, 2H, H2), 6.95-7.18 (m,
3
3
4
14H), 7.24 (ddd, 2H, JH-H ) 8.3 Hz, JH-H ) 6.6 Hz, JH-H ) 1.5
Hz), 8.10 (d, 2H, 3JH-H ) 8.1 Hz). 13C{1H} (C6D6) δ 2.47 (Si(CH3)2),
35.58 (C(CH3)3), 58.75 (C(CH3)3), 87.81 (dm, 1JC-H ) 134.0 Hz, C24/
1
1
3
C27), 106.40 (d, JC-H ) 162.2 Hz, C25/C26), 110.82 (dd, JC-H
)
2H, H4), 7.69 (td, 2H, H5), 8.18 (dm, 2H, JH-H ) 6.9 Hz, H3), 8.52
2
(dm, 2H, 3JH-H ) 7.8 Hz, H6). 13C{1H} (CD2Cl4) δ 0.44, 32.80, 65.24,
112, 32 (C1), 118.63 (C2), 123.94, 126.37, 126.97 (quat.), 127.96,
129.22, 130.85 (quat.), 133.71 (quat.). Anal. Calcd for C23H25Cl2-
NSiTi: C, 59.75; H, 5.45; N, 3.03. Found: C, 59.40; H, 5.67; N, 2.75.
172.2 Hz, JC-H ) 8.5 Hz, C2/C5), 111.19 (quat.), 123.39, 124.49,
125.40, 125.98 (quat.), 126.67, 127.11, 127.24, 127.77 (quat.), 128.22,
129.24 (quat.), 142.75 (quat.). HRMS (EI, M+): calcd for C39H39SiNTi
597.2331, found 597.2324. Anal. Calcd for C39H39SiNTi: C, 78.37;
H, 6.58; N, 2.34. Found: C, 77.55; H, 6.39; N, 1.82. The 1H and 13C-
{1H} NMR spectra of this material are shown in the Supporting
Information.
1
The H and 13C{1H} NMR spectra of this material are shown in the
Supporting Information.
Preparation of [1-[(1,2,3,3a,11b-η)-1H-Cyclopenta[l]phenanthren-
2-yl]-N-(1,1-dimethylethyl)-1,1-dimethylsilanaminato(2-)-KN]-di-
methyl-titanium (3a). In a drybox dichloro[1-[(1,2,3,3a,11b-η)-1H-
cyclopenta[l]phenanthren-2-yl]-N-(1,1-dimethylethyl)-1,1-dimethylsi-
lanaminato(2-)-κN]-titanium complex (22) (1.37 g, 2.96 mmol) was
suspended in toluene (40 mL). To this mixture MeLi (1.6 M in ether,
3.9 mL, 6.2 mmol) was added dropwise over a 1 min period while
stirring. After the addition of MeLi was completed, the solution was
stirred for 2 h. Toluene was removed under reduced pressure, and the
residue was extracted with a hot mixture of hexane (40 mL) and toluene
(7 mL). The solution was filtered hot and put into a freezer overnight.
Solvent was decanted, and the yellow crystalline material was washed
with cold hexane (3 × 10 mL) and then dried under reduced pressure
to give ca. 0.8 g of product. Solvent was removed under reduced
pressure from the decanted solution, and the residue was dissolved in
boiling hexane (20 mL) and then filtered. The solution was put into a
freezer overnight. The solvent was decanted, and the yellow crystals
were washed with cold hexane (5 mL) and then dried under reduced
Structure 1. C17H33NSiTi, Mw ) 327.43, orthorhombic, Pnma,
yellow plate (0.36 × 0.32 × 0.10 mm3), a ) 11.8100(8) Å, b )
13.3721(9) Å, c ) 12.2118(8) Å, temp ) 173(2) K, Z ) 4, V ) 1928.5-
(2) Å3, R1 ) 0.0336, 0.0398, wR2 ) 0.0951, 0.0990 (I > 2σ(I), all
data), GOF ) 1.068.
Structure of 2. C25H33NSiTi, Mw ) 423.51, monoclinic, P2(1)/c,
yellow plate (0.30 × 0.19 × 0.08 mm3), a ) 22.958(2) Å, b ) 8.1979-
(6) Å, c ) 12.4332(9) Å, â) 97.321(1)°, Z ) 4, V ) 2321.0(3) Å3,
R1 ) 0.0371, 0.0455, wR2 ) 0.0949, 0.1011 (I > 2σ(I), all data),
GOF ) 1.048.
Structure of 3a. C25H31NSiTi, Mw ) 421.50, triclinic, P1h, yellow
needle (0.21 × 0.19 × 0.11 mm3), a ) 9.2143(5) Å, b ) 12.9784(6)
Å, c ) 19.545(1) Å, R ) 84.112(1)°, â ) 77.999(1)°, γ ) 78.688(1)°,
Z ) 4, V ) 2237.2(2) Å3, R1 ) 0.0477, 0.0627, wR2 ) 0.1304, 0.1450
(I > 2σ(I), all data), GOF ) 1.031.
Structure of 3b. C39H39NSiTi, Mw ) 597.70, triclinic, P1h, brown
plate (0.05 × 0.15 × 0.30 mm3), a ) 14.282(1) Å, b ) 14.388(1) Å,
c ) 16.505(1) Å, R ) 68.603(2)°, â ) 82.910(1)°, γ ) 81.242(2)°, Z
) 4, V ) 3112.4(4) Å3, R1 ) 0.0551, 0.1389, wR2 ) 0.0808, 0.0946
(I > 2σ(I), all data), GOF ) 1.031.
1
pressure to give 0.155 g of product. Yield 76.5%. H (C6D6)) δ 0.22
(s, 6H, Si(CH3)2), 0.43 (s, 6H, Ti(CH3)2), 1.49 (s, 9H, C(CH3)3), 6.63
3
4
(s, 2H, H2), 7.32 (td, 2H, JH-H ) 7.2 Hz, JH-H ) 1.5 Hz, H5), 7.36
(td, 2H, 3JH-H ) 7.2 Hz, 4JH-H ) 1.5 Hz, H4), 7.90 (dm, 2H, 3JH-H
)
Structure of 18. C50H54K2O4, Mw ) 797.13, triclinic, P1h, yellow
needle (0.10 × 0.13 × 0.38 mm3), a ) 9.8536(6) Å, b ) 12.7084(7)
Å, c ) 18.994(1) Å, R ) 71.511(1)°, â ) 89.515(1)°, γ ) 77.149(1)°,
173(2) K, Z ) 2, V ) 2194.2(2) Å3, R1 ) 0.0550, 0.1284, wR2 )
0.1162, 0.1461 (I > 2σ(I), all data), GOF ) 0.994.
6.9 Hz, H3), 8.27 (dm, 2H, JH-H ) 7.2 Hz, H6). 13C{1H} (C6D6) δ
3
1
0.85 (Si(CH3)2), 34.57 (C(CH3)3), 56.73 (q, JC-H ) 120.06 Hz, Ti-
(CH3)2), 59.73 (C(CH3)3), 107.33 (C1), 113.72 (C2), 124.10 (C6),
125.31 (C3), 127.29 (C5), 127.55 (C4), 128.78, 129.42, 130.25. Peak
assignments were performed based on HSQC and NOESY spectra.
HRMS (EI, (M-CH3)+): calcd for C24H28SiNTi 406.1470, found
406.1473. Anal. Calcd for C25H31NSiTi: C, 71.24; H, 7.41; N, 3.32.
Found: C, 70.81; H, 7.48; N, 3.07. The 1H and 13C{1H} NMR spectra
of this material are shown in the Supporting Information.
Preparation of [1-[(1,2,3,3a,11b-η)-1H-cyclopenta[l]phenanthren-
2-yl]-N-(1,1-dimethylethyl)-1,1-dimethylsilanaminato(2-)-KN](1,4-
diphenyl-1,3-butadiene-1,4-diyl)-titanium (3b). To a warm (65 °C)
slurry of dichloro[1-[(1,2,3,3a,11b-η)-1H-cyclopenta[l]phenanthren-2-
yl]-N-(1,1-dimethylethyl)-1,1-dimethylsilanaminato(2-)-κN]-titanium (22)
(8.65 g, 0.0187 mol) and trans,trans-1,4-diphenylbutadiene (3.94 g,
0.0191 mol) in toluene (about 200 mL) was added n-BuLi (25 mL of
a 1.6 M solution, 0.040 mol). The solution darkened immediately, and
the temperature climbed to 72 °C. After ca. 45 min, the temperature
was increased to bring the mixture to reflux, and the mixture was
maintained at that temperature for 1.5 h. The mixture was cooled to
about room temperature, and the volatiles were removed under reduced
pressure. The residue was slurried in mixed hexanes (60 mL) at about
Acknowledgment. We thank Prof. Clark Landis for assistance
with magnetization transfer methodology.
Note Added After ASAP Publication. Errors in the figure
and table numbering in the Supporting Information were
corrected on May 14, 2007.
Supporting Information Available: Polymerization and NMR
data used for kinetic models; ethylene-octene polymerization
results with 1, 2, and 3a; magnetization transfer NMR data of
16 and its analysis; synthetic procedures for the preparation of
5-12 and 15-21; actual NMR spectra of compounds 2-22;
comprehensive X-ray data tables for compounds 1, 2, 3a, 3b,
and 18. This material is available free of charge via the Internet
JA070061Y
9
7076 J. AM. CHEM. SOC. VOL. 129, NO. 22, 2007