D. Zaher et al. / Journal of Organometallic Chemistry 693 (2008) 3889–3896
3895
NCH
NCH(CH
2
), 3.30 (18 H, s, N(CH
), 1.04 (12H, d, 3
HH = 6.5 Hz, NCH(CH
126 MHz, DCM-d , 298 K): d 164.4 (CArq), 145.8 (CArq), 142.3
Arq), 120.8 (CArq), 120.6 (CArH), 118.1 (CArH), 114.2 (CArH), 49.7
CH(CH ), 46.9 (CH ), 44.4 (N(CH ), 20.8 (CH(CH ). C18 Ti
382.37): C 58.53, H 9.33, N 20.48. Found C 58.60, H 9.23, N 20.57%.
3
)
2
), 3.14 (2H, sept, 3
J
HH = 6.5 Hz,
3.2.7. Synthesis of bis[2-(methoxymethyl)-benzimidazolato-
N1]Ti(NMe (7)
Following the general procedure E, reaction of 2-(methoxy-
methyl)-1H-benzimidazole (0.36 g, 2.2 mmol) and Ti(NMe
(0.33 ml, 1.23 mmol) gave 7 as an orange solid. Yield 0.74 g
13
1
3
)
2
J
3
)
2
). C{ H} NMR
j
2 2
)
(
(
(
(
2
C
2 4
)
3
)
2
2
3
)
2
3
)
2
34 6
H N
1
(74%). H NMR (500 MHz, DCM-d
2
, 293 K): d 7.73–7.71 (2H, m,
ArH), 7.53–7.52 (2H, m, ArH), 7.23–7.18 (4H, m, ArH), 5.05 (1H,
2
2
3
j
.2.4. Synthesis of [2-(Methoxymethyl)-benzimidazolato-
N1]Ti(NMe (4)
Following the general procedure C, reaction of 2-(methoxy-
methyl)-1H-benzimidazole (0.50 g, 1.42 mmol) and Ti(NMe
0.38 ml, 1.42 mmol) gave 4 as a yellow solid. Yield 1.00 g (74%).
d,
CH(H)OCH
NMR (126 MHz, toluene-d
141.9 (CArq), 121.3 (CHAr), 121.1 (CHAr), 118.3 (CHAr), 115.0 (CHAr),
74.0 (CH OCH ), 61.4 (CH OCH ), 48.7 (N(CH ). C22 Ti
J
HH = 13.0 Hz, C(H)HOCH
), 3.57 (12H, s, N(CH
, 223 K): d 157.0 (CArq), 245.9 (CArq),
3
), 5.03 (1H, d,
JHH = 13.0 Hz,
3
). C{ H}
13
1
)
2 3
3
)
3 2
), 3.17 (6H, s, OCH
8
2 4
)
(
2
3
2
3
3
)
2
30 6 2
H N O
1
H NMR (500 MHz, CDCl
3
, 298 K): d 7.67 (1H, bd, ArH), 7.17–7.10
), 3.62 (3H, s, OCH ), 3.28 (18H, s,
). C{ H} NMR (126 MHz, CDCl , 298 K): d 159.6 (CArq),
(458.38): C 57.65, H 6.60, N 18.33. Found C 57.60, H 6.56, N 18.18%.
(
3H, m, ArH), 5.12 (2H, s, OCH
2
3
1
3
1
N(CH
3
)
2
3
3.2.8. Synthesis of bis[2-(methylthioethermethyl)-benzimidazolato-
1
1
45.9 (CArq), 142.7 (CArq), 121.1 (CArH), 120.8 (CArH), 117.7 (CArH),
15.6 (CArH), 72.4 (OCH ), 60.6 (OCH ), 45.7 (N(CH ). C15 OTi
j
N1]Ti(NMe
The reaction was performed on an NMR scale following the gen-
eral procedure C in a drybox; 2-(Methylthiomethyl)-1H-benzimid-
azole (16.9 mg, 0.1 mmol) was combined with Ti(NMe (12 mg,
, 293 K): d 7.70
HH = 7.0 Hz, ArH),
7.07–7.06 (2H, bm, ArH), 6.69–6.68 (2H, bm, ArH), 4.05–4.03 (2H,
bm, NC(H)H(2/2’,b/b’)), 3.62 (12H+2H, s + bm, NCH ,b, )+NCH
(1,a)). H NMR (500 MHz, DCM-
HH = 8.0 Hz, ArH(6)), 7.62 (1H, d,
HH = 8.0 Hz, ArH(f)), 7.46–7.36 (3H, m, ArH(3,4,5)), 7.05 (1H, t,
2 2
) (8)
2
3
3
)
2
27 5
H N
(
341.17): C 52.79, H 7.97, N 20.52. Found C 52.75, H 8.01, N 20.48%.
2 4
)
1
1
3.2.5. H NMR data for in situ generated [2-(thiomethoxymethyl)-
6 6 2
0.05 mmol) in C D . H NMR (500 MHz, DCM-d
(2H, d, JHH = 8.0 Hz, ArH(6/f)), 7.20 (2H, bt, J
3
3
benzimidazolato-kN1]Ti(NMe
2
)
3
(5)
, 298 K): d 7.66 (1H, bd, ArH), 7.07–
.23 (3H, m, ArH), 3.82 (2H, s, SCH ), 3.34 (6H, s, N(CH ), 3.15
12H, s, N(CH ), 1.73 (3H, br. s, SCH ).
Generalprocedure D: A solution of the benzimidazolyl pro-ligand
in toluene (20–40 ml) was added to solution of 1 eq. of the corre-
1
H NMR (400 MHz, CDCl
3
7
(
2
)
3 2
3
(a c,x
1
)
3 2
3
(H)(2/2’,b/b’)), 2.07 (6H, s, S(CH
3
3
d
J
2
, 203 K): d 7.83 (1H, d,
J
3
o
3JHH = 8.0 Hz, ArH(e)), 6.69 (1H, d,
JHH = 8.0 Hz, ArH(d)), 5.75 (1H,
3
sponding [N,D]Ti(NMe
2
)
3
complex in toluene at À78 C. The mix-
ture was allowed to warm to room temperature over 15 h. The
solution was filtered and the solvent removed under reduced pres-
sure. The resulting solid was washed with pentane (2 Â 20 ml) and
dried under vacuum.
t, 3JHH = 8.0 Hz, ArH(c)), 4.59 (1H, d, 2JHH = 16.0 Hz, NC(H)H(b/b’)),
2
4.19 (1H, d,
N(CH )CH
NCH (CH
(3H, br, NCH
2.15 (3H, s, SCH
(126 MHz, DCM-d
146.7 (CArq(i)), 145.4 (CArq(9)), 142.8 (CArq(g)), 142.5 (CArq(7)),
121.5 (CArH(3/4/5)), 121.0 (CArH(3/4/5)), 120.6 (CArH(d)), 120.1
(CArH(e)), 118.1 (CArH(6)), 117.3 (CArH(f)), 115.2 (CArH(3/4/5)),
J
HH = 16.0 Hz, NCH(H)(b/b’)), 3.85 (3H, br,
)CH /b)), 3.53 (3H, br,
HH = 16.0 Hz, NC(H)H(2/2’)), 3.28
3
3
(
c
a
/
x
)), 3.61 (3H, br, N(CH
3
3
(a
2
3
3
)(
/b)), 3.45 (1H, d,
(CH )( )), 2.75 (1H, d,
(a)), 1.85 (3H, s, SCH
, 203 K): d 161.9 (CArq(h)), 160.8 (CArq(8)),
J
2
Generalprocedure E: A solution benzimidazolyl pro-ligand in tol-
3
3
c
/x
JHH = 16 Hz, NC(H)H(2/2’)),
1
3
1
uene (20–40 ml) was added to solution of ½ eq. of Ti(NMe
2
)
4
in tol-
3
3
(1)).
C{ H} NMR
o
uene at À78 C. The mixture was allowed to warm to room
temperature over 15 h, filtered, and the solvent was removed un-
der reduced pressure. The resulting solid was washed with pentane
8
(
2 Â 20 ml) and dried under vacuum.
1
13.9 (CArH(c)), 53.44 (N(CH
(N(CH )), 42.4 (N(CH /b)), 35.6 (NCH(b/b’)), 35.0 (NCH(2/
2’)), 18.2 (SCH (a)), 16.7 (SCH (1)).
3 3
(c/x)), 51.4 (N(CH (a/b)), 46.3
3.2.6. Synthesis of bis[2-(dimethylaminomethyl)-benzimidazolato-
3
(c
/x
3
(a
j
N1]Ti(NMe (6)
Following the general procedure D, reaction of 2-(dimethylami-
nomethyl)-1H-benzimidazole (0.21 g, 1.2 mmol) and 1 (0.43 ml,
)
2 2
3
3
3.3. Ethylene polymerization procedure
1
1
.2 mmol) gave 6 as a red solid. Yield 0.51 g (88%). H NMR
500 MHz, toluene-d HH = 8.0 Hz, ArH(7/
, 293 K): d 7.96 (2H, d, 3
g)), 7.14–7.12 (2H, m, ArH), 7.05–7.03 (2H, m, ArH), 6.69–6.67
(
8
J
A known quantity of pre-catalyst (5–10 mg) was transferred to
a Schlenk flask in a glove-box. Toluene was added (100 ml), fol-
lowed by a known amount of aluminium alkyl (TMA, TIBAL) and
the mixture stirred at room temperature for 15 min. The co-cata-
lyst (MAO, DMAO) was added and the vessel placed in a water bath
at the desired temperature and the Schlenk was flushed with
0.5 bar of ethylene (1.5 bar overall pressure). Polymerizations were
terminated by venting the overpressure, and addition of 10 ml 2 M
HCl(aq). The polyethylene was precipitated from the reaction mix-
ture by addition of MeOH (200 ml). After filtration the polymer
was washed with a large quantity of MeOH and dried under vac-
uum at 60 °C for 12 h.
2
(
(
1H, bm, ArH), 3.39 (2H, d,
2H, bd,
J
HH = 14.0 Hz NCH(H)(c’/c, 2’/2), 3.29
2
JHH = 14.0 Hz NC(H)H (c’/c, 2’/2)), 2.88 (12H, s,
1
NCH
ene-d
(a,b,c)), 1.63 (6H, s, NCH (a/b, 1/2)). H NMR (500 MHz, tolu-
3 3
3
8
, 223K): d 8.23 (1H, d, JHH = 8.0 Hz, ArH(7)), 8.04 (1H, d,
3
HH = 8.0 Hz, ArH(g)), 7.42 (1H, t, 3JHH = 8.0 Hz, ArH(5)), 7.36 (1H,
J
t, 3JHH = 8.0 Hz, ArH(6)), 7.26 (1H, d,
3
J
HH = 8.0 Hz, ArH(4)), 7.08
3
3
(
1H, t,
J
HH = 8.0 Hz, ArH(f)), 6.86 (1H, t,
J
HH = 8.0 Hz, ArH(e)),
3
2
6
.25 (1H, d,
J
HH = 8.0 Hz, ArH(d)), 3.71 (1H, d,
J
HH = 14.0 Hz,
HH = 14.0 Hz, NC(H)(3)H(3’)), 3.37
HH = 14.0 Hz, NCH(c)H(c’)), 3.06 (3H, s, NCH /b)), 2.85
HH = 14.0 Hz, NC(H)(3’)H(3)), 2.81 (3H, s, NCH /b)),
)), 1.81 (3H, s, NCH (b)), 1.56 (3H, s, N
(a)), 1.32 (3H, s, NCH (2)), 1.22 (3H, s, NCH
, 223 K): d 160.5 (CArq(i)), 160.2 (CArq(9)),
47.0 (CArq(j)), 146.6 (CArq(10)), 143.7 (CArq(h)), 143.6 (CArq(8)),
2
NC(H)(c’)H(c)), 3.47 (1H, d,
J
2
(
(
1H, d,
1H, d,
J
3
(a
2
J
3
(a
2
CH
.56 (6H, br, NCH
3
(
c
3
Acknowledgment
(1)). 13C{ H} NMR
1
3
3
3
(
126 MHz, toluene-d
8
Ineos Technologies is thanked for financial support of this work.
1
1
1
6
5
C
7
22.0 (CArH(e)), 121.6 (CArH(6)), 121.4 (CArH(5)), 121.0 (CArH(f)),
19.8 (CArH(7)), 118.7 (CArH(g)), 115.5 (CArH(4)), 114.9 (CArH(d)),
3.5 (NCH(c)), 63.0 (NCH(3)), 53.3 (N(CH
0.4 (NCH (a)), 47.9 (NCH (2)), 47.7 (NCH
Ti (484.46): C 59.50, H 7.49, N 23.13. Found C 59.58, H
.39, N 22.91%.
Appendix A. Supplementary material
3
3
(a/b)), 50.7 (NCH (b)),
CCDC 671182, 671184, 671185 and 671183 contain the supple-
mentary crystallographic data for compounds 4, 6, 7 and A. These
data can be obtained free of charge from The Cambridge Crystallo-
3
3
3 3
(1)), 47.0 (N(CH (a/b)).
24
36 8
H N