Cationic Methyltitanium Phosphinimides
Organometallics, Vol. 24, No. 6, 2005 1093
(s, 9H, 4-t-Bu), 1.27 (s, 3H, TiMe), 0.48 (br s, 3H, MeB).13C-
9H, Me), 1.40 (d, 27 H, 3JP-H ) 14 Hz, t-Bu), 1.17 (s, 3H, TiMe),
1
1
{1H} NMR: 148.8 (d m, JCF ) 230 Hz, C6F5 (o-C)), 147.2 (s,
0.50 (br s, 3H, MeB). 13C{1H} NMR: 148.9 (d m, JCF ) 235
1
4
C5H4N (R-C)), 137.9 (d m), JCF ) 250 Hz, C6F5 (p-C)), 137.0
Hz, C6F5 (o-C)), 143.2 (d, JPC ) 2 Hz, P(p-CH3C6H4) (p-C)),
1
(d m, JCF ) 253 Hz, C6F5 (m-C)), 128.6 (br s, C6F5 (ipso-C)),
138.1 (d m), 1JCF ) 243 Hz, C6F5 (p-C)), 137.0 (ddd, 1JCF ) 247
1
2
3
2
123.4 (s, C5H4N), 115.4 (s, Cp), 54.4 (s, TiMe), 42.1 (d, JPC
)
Hz, JCF ) 23 Hz, JCF ) 11 Hz, C6F5 (m-C)), 134.1 (d, JPC )
43 Hz, t-Bu), 35.4 (s, t-Bu), 30.3 (s, t-Bu), 29.8 (s, t-Bu), 10.7
13 Hz, C6H4 (o-C)), 130.8 (d, 3JPC ) 10 Hz, C6H4 (m-C)), 129.2
(br s, C6F5 (ipso-C)), 125.8 (d, JPC ) 38 Hz, C6H4 (ipso-C)),
1
1
(br q, JBC ) 54 Hz, MeB). 11B{1H} NMR: -15.1. 19F NMR:
-133.4 (d, 6F, 3JFF ) 22 Hz, C6F5 (o-F)), -165.6 (t, 3F, 3JFF
)
115.8 (s, Cp), 65.1 (d, JPC ) 5 Hz, TiMe), 42.2 (d, JPC ) 42
2
1
3
21 Hz, C6F5 (p-F)), -168.1 (t, 6F, JFF ) 20 Hz, C6F5 (m-F)).
31P{1H} NMR: 51.1. Anal. Calcd for C46H51BF15N2PTi: C,
54.89, H, 5.11, N, 2.78. Found: C, 54.79, H, 4.99, N, 2.43. 8:
yellow solid (65 mg, 93%). 1H NMR: 7.62 (d, 2H, 3JHH ) 7 Hz,
Hz, t-Bu), 30.0 (s, t-Bu), 21.7 (s, Me), 10.6 (br q, 1JBC ) 54 Hz,
MeB). 11B{1H} NMR: -15.2. 19F NMR: -133.7 (d, 6F, JFF
)
3
3
20 Hz, C6F5 (o-F)), -165.6 (t, 3F, JFF ) 20 Hz, C6F5 (p-F)),
-168.1 (t, 6F, JFF ) 20 Hz, C6F5 (m-F)). 31P{1H} NMR: 53.6
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3
C5H4N, (R-H)), 6.52 (d, 2H, JHH ) 7 Hz, C5H4N, (â-H)), 6.37
(s, NP), 13.6 (s, TiP). Anal. Calcd for C58H59BF15NP2Ti: C,
3
(s, 5H, Cp), 3.07 (s, 6H, 4-Me2N), 1.46 (d, 27H, JPH ) 14 Hz,
59.25, H, 5.06, N, 1.19. Found: C, 59.02, H, 4.93, N, 1.01. 13:
t-Bu), 1.10 (s, 3H, TiMe), 0.48 (br s, 3H, MeB). 13C{1H} NMR:
yellow solid (147 mg, 93%). H NMR: 8.20 (s, br, 2H, Py (R-
1
1
3
3
155.9 (s, C5H4N, (γ-C)), 148.7 (d m, JCF ) 255 Hz, C6F5 (o-
H)), 8.05 (t, 1H, JHH ) 8 Hz, Py (γ-H)), 7.61 (t, 2H, JHH ) 7
1
3
C)), 146.9 (s, C5H4N, (R-C)), 138.0 (d m, JCF ) 233 Hz, C6F5
Hz, Py (â-H)), 6.46 (s, 5H, Cp), 1.46 (d, 27H, JPH ) 14 Hz,
1
1
(p-C)), 136.9 (d m, JCF ) 234 Hz, C6F5 (m-C)), 128.6 (br s,
t-Bu), 1.29 (s, 3H, TiMe). 13C{1H} NMR: 148.8 (d m, JCF
)
C6F5 (ipso-C)), 114.7 (s, Cp), 107.3 (s, C5H4N, (â-C)), 52.1 (s,
240 Hz, C6F5 (o-C)), 148.0 (s, Py (R-C)), 142.4 (s, Py (γ-C)), 138.9
1
1
1
TiMe), 42.1 (d, JPC ) 43 Hz, t-Bu), 39.8 (s, Me2N), 29.8 (s,
(d m, JCF ) 243 Hz, C6F5 (p-C)), 136.9 (d m, JCF ) 247 Hz,
C6F5 (m-C)), 127.0 (s, Py (â-C)), 124.8 (br s, C6F5 (ipso-C)), 115.5
1
t-Bu), 10.7 (br q, JBC ) 54 Hz, MeB). 11B{1H} NMR: -15.2.
3
1
19F NMR: -133.4 (d, 6F, JFF ) 22 Hz, C6F5 (o-F)), -165.5 (t,
(s, Cp), 54.9 (s, TiMe), 42.2 (d, JPC ) 43 Hz, t-Bu), 29.7 (s,
3
3
3F, JFF ) 21 Hz, C6F5 (p-F)), -168.2 (t, 6F, JFF ) 20 Hz,
C6F5 (m-F)). 31P{1H} NMR: 49.1. Anal. Calcd for C46H48BF15N3-
PTi: C, 54.30, H, 4.75, N, 4.13. Found: C, 54.09, H, 4.25, N,
4.01. 9: yellow solid (50 mg, 75%). 1H NMR: 6.45 (s, 5H, Cp),
t-Bu). 11B{1H} NMR: -16.8. 19F NMR: -133.2 (s, 8F, C6F5 (o-
3
F)), -163.9 (t, 4F, JFF ) 21 Hz, C6F5 (p-F)), -167.7 (t, 8F,
3JFF ) 17 Hz, C6F5 (m-F)). 31P{1H} NMR: 51.7. Anal. Calcd
for C47H40BF20N2PTi: C, 51.20, H, 3.66, N, 2.54. Found: C,
51.07, H, 3.32, N, 2.27. 14: yellow solid (72 mg, 91%). 1H
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2
1.54 (d, 27H, JP-H ) 14 Hz, t-Bu), 1.37 (d, 9H, JPH ) 8 Hz,
PMe), 0.80 (s, 3H, TiMe), 0.48 (br s, 3H, MeB). 13C{1H} NMR:
148.7 (d m, 1JCF ) 238, C6F5 (o-C)), 138.1 (d m, 1JCF ) 243 Hz,
C6F5 (p-C)), 136.9 (ddd, JCF ) 245 Hz, JCF ) 24 Hz, JCF
12 Hz, C6F5 (m-C)), 129.2 (br s, C6F5 (ipso-C)), 114.9 (s, Cp),
3
NMR: 8.16 (d, 2H, JHH ) 6 Hz, C5H4N (â-H)), 7.23 (d, 2H,
3JHH ) 7 Hz, C5H4N (R-H)), 6.44 (d, 5H, Cp), 2.78 (q, 2H, 3JHH
1
2
3
3
)
) 8 Hz, Et), 1.45 (d, 27H, JPH ) 14 Hz, t-Bu), 1.27 (t, 3H,
3JHH ) 8 Hz, Et), 1.24 (s, 3H, TiMe). 13C{1H} NMR: 160.0 (s,
C5H4N (γ-C)), 148.8 (d m, 1JCF ) 240 Hz, C6F5 (o-C)), 148.0 (s,
2
1
63.9 (d, JPC ) 5 Hz, TiMe), 42.0 (d, JPC ) 43 Hz, t-Bu), 30.0
(s, t-Bu), 26.4 (d, 1JPC ) 23 Hz, PMe), 10.6 (br q, 1JBC ) 54 Hz,
C5H4N (R-C)), 138.9 (d m), JCF ) 240 Hz, C6F5 (p-C)), 137.0
1
MeB). 11B{1H} NMR: -15.2. 19F NMR: -133.7 (d, 6F, JFF
)
(d m, 1JCF ) 240 Hz, C6F5 (m-C)), 126.2 (s, C5H4N (â-C), 124.6
(br s, C6F5 (ipso-C)), 115.5 (s, Cp), 54.6 (s, TiMe), 42.2 (d, 1JPC
) 43 Hz, t-Bu), 29.9 (s, t-Bu), 29.1 (s, Et), 13.9 (s, Et). 11B{1H}
NMR: -16.8. 19F NMR: -133.3 (s, 6F, C6F5 (o-F)), -163.9 (t,
3F, 3JFF ) 20 Hz, C6F5 (p-F)), -167.7 (m, 6F, C6F5 (m-F)). 31P-
{1H} NMR: 51.2. Anal. Calcd C49H44BF20N2PTi: C, 52.06, H,
3.92, N, 2.48. Found: C, 51.88, H, 3.64, N, 2.12. 15: yellow
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3
20 Hz, C6F5 (o-F)), -165.6 (t, 3F, JFF ) 20 Hz, C6F5 (p-F)),
-168.1 (m, 6F, 3JFF ) 20 Hz, C6F5 (m-F)). 31P{1H} NMR: 52.1
(s, NP), -18.6 (s, PMe3). Anal. Calcd for C40H47BF15NP2Ti: C,
50.71, H, 5.00, N, 1.48. Found: C, 50.35, H, 4.69, N, 1.39. 10:
bright yellow solid (112 mg, 61%). H NMR: 6.44 (d, 5H,3JPH
1
3
) 1 Hz, Cp), 1.76 (m, 6H, PCH2), 1.56 (d, 27H, JPH ) 14 Hz,
1
t-Bu), 1.38 (m, 6H, PCH2CH2), 1.29 (m, 6H, CH2Me), 0.94 (t,
solid (70 mg, 86%). H NMR: 8.06 (br s, 2H, C5H4N, (R-H)),
3
9H, JHH ) 7 Hz, CH2Me), 0.83 (s, 3H, TiMe), 0.50 (br s, 3H,
7.56 (br s, 2H, C5H4N, (â-H)), 6.44 (s, 5H, Cp), 1.44 (d, 27 H,
3JP-H ) 14 Hz, t-Bu), 1.32 (s, 9H, t-Bu), 1.27 (s, 3H, TiMe).
13C{1H} NMR: 160.0 (s, C5H4N (γ-C)), 148.8 (d m, 1JCF ) 235
Hz, C6F5 (o-C)), 147.7 (s, C5H4N (R-C)), 138.8 (d m, 1JCF ) 246
Hz, C6F5 (p-C)), 136.9 (d m), 1JCF ) 250 Hz, C6F5 (m-C)), 125.2
(br s, C6F5 (ipso-C)), 123.8 (s, C5H4N (â-C)), 115.4 (s, Cp), 54.5
MeB). 13C{1H} NMR: 148.9 (d m, JCF ) 120 Hz, JCF ) 14
1
2
Hz, C6F5 (o-C)), 138.1 (d m, 1JCF ) 240 Hz, C6F5 (p-C)), 137.0
(ddd, JCF ) 250 Hz,2JCF ) 24 Hz, JCF ) 11 Hz, C6F5 (m-C)),
1
3
129.2 (br, C6F5 (ipso)), 114.6 (s, Cp), 64.1 (d,2JPC ) 5 Hz, TiMe),
1
42.1 (d, JPC ) 43 Hz, t-Bu), 30.1 (s, t-Bu), 26.4 (s, CH2CH2),
2
3
1
25.0 (d, JPC ) 13 Hz, PCH2), 24.3 (d, JPC ) 18 Hz, PCH2-
(s, TiMe), 42.2 (d, JPC ) 43 Hz, t-Bu), 34.7 (s, t-Bu), 30.2 (s,
CH2), 13.7 (s, CH2Me), 10.6 (br q, JB-C ) 54 Hz, MeB). 11B-
t-Bu), 29.8 (s, t-Bu). 11B{1H} NMR: -16.8. 19F NMR: -133.2
{1H} NMR: -15.2. 19F NMR: -133.34 (d, 6F, JFF ) 20 Hz,
(s, 8F, C6F5 (o-F)), -163.9 (t, 4F, JFF ) 20 Hz, C6F5 (p-F)),
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3
C6F5 (o-F)), -165.64 (t, 3F, 3JFF ) 20 Hz, C6F5 (p-F)), -168.15
(m, 6F, C6F5 (m-F)). 31P{1H} NMR: 52.1 (s, NP), 3.0 (s, Pn-
Bu3). Anal. Calcd for C49H65BF15NP2Ti: C, 54.82, H, 6.10, N,
1.30. Found: C, 54.54, H, 5.88, N, 1.08. 11: bright yellow solid
-167.7 (br s, 8F, C6F5 (m-F)). 31P{1H} NMR: 51.1. Anal. Calcd
for C51H48BF20N2PTi: C, 52.87, H, 4.18, N, 2.41. Found: C,
52.66, H, 3.87, N, 2.23. 16: yellow solid (66 mg, 82%). 1H
3
NMR: 7.65 (d, 2H, JHH ) 7 Hz, C5H4N, (R-H)), 6.53 (d, 2H,
1
(69 mg, 87%). H NMR: 7.54 (m, 9H, PPh (o,p-H)), 7.39 (t m,
3JHH ) 7 Hz, C5H4N), (â-H)), 6.38 (s, 5H, Cp), 3.08 (s, 6H,
4-Me2N), 1.48 (d, 27 H, 3JPH ) 14 Hz, t-Bu), 1.12 (s, 3H, TiMe).
13C{1H} NMR: 155.9 (s, C5H4N, (γ-C)), 148.8 (d m, 1JCF ) 253
3
3
6H, JP-H ) 2 Hz, PPh (m-H)), 6.31 (d, 5H, JPH ) 1 Hz, Cp),
1.41 (d, 27 H, 3JPH ) 14 Hz, t-Bu), 1.20 (s, 3H, TiMe), 0.50 (br
s, 3H, MeB). 13C{1H} NMR: 148.8 (d m, JCF ) 232 Hz, C6F5
C6F5 (o-C)), 147.0 (s, C5H4N, (R-C)), 138.9 (d m), JCF ) 245
1
1
(o-C)), 138.0 (d m, 1JCF ) 245 Hz, C6F5 (p-C)), 136.9 (ddd, 1JCF
Hz, C6F5 (p-C)), 137.0 (d m, 1JCF ) 238 Hz, C6F5 (m-C)), 125.1
(br s, C6F5 (ipso-C)), 114.6 (s, Cp), 107.4 (s, C5H4N, (â-C)), 52.3
(s, TiMe), 42.2 (d, 1JPC ) 43 Hz, t-Bu), 39.7 (s, Me2N), 29.9 (s,
t-Bu). 11B{1H} NMR: -16.8. 19F NMR: -133.3 (s, 8F, C6F5 (o-
F)), -163.9 (t, 4F, 3JFF ) 20 Hz, C6F5 (p-F)), -167.7 (br s, 8F,
C6F5 (m-F)). 31P{1H} NMR: 48.9. Anal. Calcd for C49H45BF20N3-
PTi: C, 51.38, H, 3.96, N, 3.67. Found: C, 51.23, H, 3.59, N,
2
3
) 246 Hz, JCF ) 23 Hz, JCF ) 12 Hz, C6F5 (m-C)), 134.2 (d,
2JPC ) 12 Hz, PPh, (o-C)), 132.5 (d, JPC ) 2 Hz, PPh, (p-C)),
4
3
1
130.2 (d, JPC ) 10 Hz, PPh, (m-C)), 128.0 (d, JPC ) 36 Hz,
PPh (ipso-C)), 129.2 (br s, C6F5 (ipso-C)), 115.9 (s, Cp), 65.7
2
1
(d, JPC ) 5 Hz, TiMe), 42.2 (d, JPC ) 42 Hz, t-Bu), 30.0 (s,
t-Bu), 10.4 (br q, JBC ) 54 Hz, MeB). 11B{1H} NMR: -15.2.
1
19F NMR: -133.4 (d, 6F, JFF ) 22 Hz, C6F5 (o-F)), -165.6 (t,
3.39. 17: bright yellow solid (58 mg, 75 %). H NMR: 6.45 (s,
3
1
3
3
3F, JFF ) 21 Hz, C6F5 (p-F)), -168.1 (t, 6F, JFF ) 20 Hz,
C6F5 (m-F)). 31P{1H} NMR: 54.3 (s, NP), 15.1 (s, PPh3). Anal.
Calcd for C55H53BF15NP2Ti: C, 58.27, H, 4.71, N, 1.24.
Found: C, 58.01, H, 4.58, N, 1.11. 12: yellow solid (72 mg,
87%). 1H NMR: 7.30 (m, 12H, C6H4), 6.29 (s, 5H, Cp), 2.41 (s,
5H, Cp), 1.55 (d, 27H, 3JPH ) 14 Hz, t-Bu), 1.37 (d, 9H, 2JPH
)
8 Hz, PCH3), 0.80 (s, 3H, TiMe). 13C{1H} NMR: 148.3 (d m,
1
1JCF ) 244 Hz, C6F5 (o-C)), 138.5 (d m, JCF ) 234 Hz, C6F5
(p-C)), 136.5 (ddd, 1JCF ) 240 Hz, 2JCF ) 24 Hz, 3JCF ) 11 Hz,
C6F5 (m-C)), 124.0 (br s, C6F5 (ipso-C)), 114.8 (s, Cp), 63.9 (s,