2444 Organometallics, Vol. 23, No. 10, 2004
Matsushima et al.
2.14 (s, 3H, CH3), 1.52 (dd, 3H, J ) 6.3, 1.6 Hz, CH3), 0.07
(ddd, 1H, J ) 15.4, 9.3, 2.2 Hz, H2 or H3), 0.01 (dq, 1H, J )
21.2, 6.3 Hz, H2 or H3). 31P NMR (160 MHz): δ 49.2.
2.21 (d, 3H, J ) 1.4 Hz, Cp′Me), 1.40 (t, 1H, J ) 11.0 Hz, H2
or H3), 0.62-0.58 (m, 1H, H2 or H3). 31P NMR (160 MHz): δ
45.3.
[(η5:η1-2-Me -4-P h C5H 2CO2CH 2CH 2P P h 2)R u {η4-CH 2d
CHC(P h )dCH2}][P F 6] (9b). IR (cm-1, KBr): 1738 (νCdO).
HRMS calcd for C37H34O2PRu (M - PF6-) 643.1340, found m/z
643.1360. For major product 9b-I: 1H NMR (600 MHz): δ
8.25-7.38 (m, 20H, Ph), 6.71 (t, 1H, J ) 9.3 Hz, H6), 5.82 (s,
1H, Cp′), 5.76 (q, 1H, J ) 1.7 Hz, Cp′), 5.26 (ddd, 1H, J )
23.9, 11.5, 6.9 Hz, OCH2), 4.52 (ddt, 1H, J ) 11.5, 5.2, 2.2 Hz,
OCH2), 4.22 (s, 1H, H1 or H4), 3.57-3.45 (m, 2H, PCH2), 2.61
(ddd, 1H, J ) 8.0, 2.2, 1.4 Hz, H1 or H4), 1.09 (d, 3H, J ) 1.7
Hz, CH3), -0.08 (ddd, 1H, J ) 15.1, 9.3, 2.2 Hz, H2 or H3),
-0.21 (dd, 1H, J ) 16.8, 2.7 Hz, H2 or H3). 31P NMR (160
MHz): δ 53.0. For minor product 9b-II: 31P NMR (160 MHz):
δ 51.8.
[(η5:η1-2-Me -4-P h C5H 2CO2CH 2CH 2P P h 2)R u {η4-CH 2d
C(Me)CHdCHMe}][P F 6] (10b). IR (cm-1, KBr): 1733 (νCdO).
HRMS calcd for C33H34O2PRu (M - PF6-) 595.1340, found m/z
595.1339. For major product: 10b-I: 1H NMR (400 MHz): δ
7.95-7.39 (m, 15H, Ph), 6.12 (s, 1H, Cp′), 5.80 (dd, 1H, J )
4.1, 2.4 Hz, Cp′), 5.70 (d, 1H, J ) 9.0 Hz, H5), 5.29 (ddd, 1H,
J ) 22.7, 11.7, 7.1 Hz, OCH2), 4.55 (ddt, 1H, J ) 11.7, 5.1, 2.2
Hz, OCH2), 3.46-3.25 (m, 2H, PCH2), 2.74 (s, 1H, H4), 2.48
(d, 3H, J ) 1.7 Hz, Me), 2.45 (s, 3H, Me), 1.64 (d, 3H, J ) 6.1
Hz, Me), 0.53-0.43 (m, 1H, H2 or H3), -0.44 (dd, 1H, J ) 16.6,
2.2 Hz, H2 or H3). 31P NMR (160 MHz): δ 50.7. For minor
product 10b-II: 1H NMR (400 MHz): δ 7.95-7.39 (m, 15H,
Ph), 6.34 (s, 1H, Cp′), 5.96 (t, 1H, J ) 2.7 Hz, Cp′), 5.61 (d,
1H, J ) 9.5 Hz, H6), 5.22-5.17 (m, 1H, OCH2), 4.40-4.32 (m,
1H, OCH2), 3.46-3.25 (m, 2H, PCH2), 3.11 (s, 1H, H1), 2.58
(s, 3H, CH3), 2.28 (d, 3H, J ) 1.5 Hz, CH3), 0.72 (dd, 3H, J )
6.1, 1.7 Hz, CH3), 0.22-0.14 (m, 1H, H2 or H3), -0.10 to -0.14
(m, 1H, H2 or H3). 31P NMR (160 MHz): δ 50.4.
[(η5:η1-2-Me -4-P h C5H 2CO2CH 2CH 2P P h 2)R u {η4-CH 2d
CHC(Me)dCHMe}][P F 6] (11b). IR (cm-1, KBr): 1731 (νCdO).
HRMS calcd for C33H34O2PRu (M - PF6-) 595.1340, found m/z
595.1339. For major product 11b-I: 1H NMR (400 MHz): δ
7.88-7.39 (m, 15H, Ph), 6.29 (s, 1H, Cp′), 5.80 (t, 1H, J ) 8.5
Hz, H6), 5.66 (dd, 1H, J ) 4.1, 2.4 Hz, Cp′), 5.29 (ddd, 1H, J )
22.7, 11.7, 7.3 Hz, OCH2), 4.50 (ddt, 1H, J ) 11.7, 5.1, 3.5 Hz,
OCH2), 3.49-3.30 (m, 2H, PCH2), 2.55 (s, 3H, Me), 2.33 (d,
3H, J ) 1.7 Hz, Me), 2.15 (d, 1H, J ) 8.1 Hz, H4), 1.57 (dd,
3H, J ) 6.3, 1.5 Hz, Me), 0.34-0.25 (m, 1H, H2 or H3), -0.26
(ddd, 1H, J ) 15.9, 9.8, 2.2 Hz, H2 or H3). 31P NMR (160
MHz): δ 51.8. For minor product 11b-II: 1H NMR (400
MHz): δ 7.88-7.39 (m, 15H, Ph), 6.13 (s, 1H, Cp′), 6.01 (dd,
1H, J ) 3.7, 2.4 Hz, Cp′), 5.56 (t, 1H, J ) 8.2 Hz, H5), 5.21-
5.18 (m, 1H, OCH2), 4.43-4.38 (m, 1H, OCH2), 3.49-3.30 (m,
2H, PCH2), 2.99 (d, 1H, J ) 7.5 Hz, H1), 2.39 (s, 3H, Me), 2.31
(d, 3H, J ) 1.5 Hz, Me), 0.83 (dd, 3H, J ) 6.1, 1.7 Hz, Me),
0.13-0.02 (m, 2H, H2 and H3). 31P NMR (160 MHz): δ 49.3.
[(η5:η1-2-Me -4-Bu t C5H 2CO2CH 2CH 2P P h 2)R u (η4-CH 2d
CHCHdCHMe)][P F 6] (4c). IR (cm-1, KBr): 1731 (νCdO). FAB
MS: m/z 561 (M - PF6-). Anal. Calcd for C30H36F6O2P2Ru: C,
51.07; H, 5.14. Found: C, 50.80; H, 5.05. For major product
4c-I: 1H NMR (400 MHz): δ 8.18-8.13 (m, 2H, Ph), 7.76-
7.65 (m, 4H, Ph), 7.41 (br, 4H, Ph), 6.14-6.07 (m, 1H, H5 or
H6), 5.85 (s, 1H, Cp′), 5.74 (dd, 1H, J ) 9.8, 5.4 Hz, H5 or H6),
5.33-5.22 (m, 2H, CpH, OCH2), 4.44-4.40 (m, 1H, OCH2), 3.71
(d, 1H, J ) 7.8 Hz, H4), 3.42-3.24 (m, 2H, PCH2), 2.33 (d, 3H,
J ) 1.7 Hz, Cp′Me), 1.64 (d, 3H, J ) 6.1 Hz, Me on diene),
1.34 (s, 9H, But), 0.59-0.50 (m, 1H, H2 or H3), -0.29 to -0.35
(m, 1H, H2 or H3). 31P NMR (160 MHz): δ 46.3. For minor
product 4c-II: 1H NMR (400 MHz): δ 8.18-8.13 (m, 2H, Ph),
7.76-7.65 (m, 4H, Ph), 7.41 (br, 4H, Ph), 6.14-6.07 (m, 1H,
H5 or H6), 5.83 (s, 1H, Cp′), 5.55 (t, 1H, J ) 2.4 Hz, Cp′), 5.33-
5.22 (m, 2H, H5 or H6 and OCH2), 4.44-4.40 (m, 1H, OCH2),
[(η5:η1-2-Me -4-P h C5H 2CO2CH 2CH 2P P h 2)R u (η4-CH 2d
CHCHdCHMe)][P F 6] (4b). IR (cm-1, KBr): 1732 (νCdO). FAB
MS: m/z 581 (M - PF6-). Anal. Calcd for C32H32F6O2P2Ru: C,
52.97; H, 4.45. Found: C, 52.71; H, 4.22. For major product
4b-I: 1H NMR (400 MHz): δ 7.90-7.40 (m, 15H, Ph), 6.46 (s,
1H, Cp′), 6.14-6.09 (m, 1H, H5 or H6), 5.88 (dd, 1H, J ) 10.3,
5.6 Hz, H5 or H6), 5.76 (dd, 1H, J ) 4.2, 2.4 Hz, Cp′), 5.37-
5.19 (m, 1H, OCH2), 4.54 (dq, 1H, J ) 4.2, 2.4 Hz, OCH2),
3.46-3.24 (m, 2H, PCH2), 2.79 (s, 1H, H4), 2.45 (d, 3H, J )
1.7 Hz, Cp′Me), 1.64 (d, 3H, J ) 6.1 Hz, Me on diene), 0.72-
0.61 (m, 1H, H2 or H3), -0.26 (dd, 1H, J ) 12.2, 11.0 Hz, H2
or H3). 31P NMR (160 MHz): δ 50.8. For minor product 4b-II:
1H NMR (400 MHz): δ 7.90-7.40 (m, 15H, Ph), 6.54 (s, 1H,
Cp′), 6.05 (dd, 1H, J ) 4.2, 2.4 Hz, Cp′), 5.96 (dd, 1H, J )
10.3, 5.6 Hz, H5 or H6), 5.73-5.69 (m, 1H, H5 or H6), 5.37-
5.19 (m, 1H, OCH2), 4.45 (dt, 1H, J ) 5.4, 2.0 Hz, OCH2), 3.46-
3.24 (m, 2H, PCH2), 3.05 (d, 1H, J ) 6.8 Hz, H1), 2.28 (d, 3H,
J ) 1.7 Hz, Cp′Me), 0.78 (dd, 3H, J ) 6.1, 1.5 Hz, Me on diene),
0.35-0.25 (m, 1H, H2 or H3), -0.12 (dd, 1H, J ) 10.5, 12.4
Hz, H2 or H3). 31P NMR (160 MHz): δ 49.3.
[(η5:η1-2-Me -4-P h C5H 2CO2CH 2CH 2P P h 2)R u (η4-CH 2d
CHCHdCHEt)][P F 6] (5b). IR (cm-1, KBr): 1733 (νCdO). FAB
MS: m/z 595 (M - PF6-). Anal. Calcd for C33H34F6O2P2Ru: C,
53.59; H, 4.63. Found: C, 53.88; H, 4.69. For major product
5b-I: 1H NMR (400 MHz): δ 7.89-7.41 (m, 15H, Ph), 6.45 (s,
1H, Cp′), 6.12-6.06 (m, 1H, H5 or H6), 5.88 (dd, 1H, J ) 9.8,
5.4 Hz, H5 or H6), 5.76 (dd, 1H, J ) 3.9, 2.4 Hz, Cp′), 5.35-
5.19 (m, 1H, OCH2), 4.53 (ddt, 1H, J ) 9.3, 5.1, 2.2 Hz, OCH2),
3.47-3.29 (m, 2H, PCH2), 3.05 (d, 1H, J ) 8.1 Hz, H1), 2.44
(d, 3H, J ) 1.7 Hz, Cp′Me), 1.76-1.68 (m, 1H, CH2CH3), 1.13-
1.05 (m, 3H, CH2CH3), 0.26-0.22 (m, 1H, H2 or H3), -0.18 to
-0.22 (m, 1H, H2 or H3). 31P NMR (160 MHz): δ 50.6. Minor
product 5b-II: 1H NMR (400 MHz): δ 7.89-7.41 (m, 15H, Ph),
6.52 (s, 1H, Cp′), 6.04 (dd, 1H, J ) 3.4, 2.4 Hz, Cp′), 6.00 (dd,
1H, J ) 9.8, 5.4 Hz, H5 or H6), 5.73-5.69 (m, 1H, H5 or H6),
5.35-5.19 (m, 1H, OCH2), 4.39 (ddt, 1H, J ) 9.5, 5.1, 2.2 Hz,
OCH2), 3.47-3.29 (m, 3H, PCH2, H1), 2.27 (d, 3H, J ) 1.7 Hz,
Cp′Me), 1.29-1.26 (m, 2H, CH2CH3), 0.65-0.53 (m, 4H,
CH2CH3 and H2 or H3), 0.18-0.12 (m, 1H, H2 or H3). 31P NMR
(160 MHz): δ 49.4.
[(η5:η1-2-Me -4-P h C5H 2CO2CH 2CH 2P P h 2)R u {η4-CH 2d
CHC(Me)dCH2}][P F 6] (6b). IR (cm-1, KBr): 1727 (νCdO).
FAB MS: m/z 581 (M - PF6-). Anal. Calcd for C32H32F6O2-
P2Ru: C, 52.97; H, 4.45. Found: C, 52.74; H, 4.25. For major
product 6b-I: 1H NMR (400 MHz): δ 7.78-7.57 (m, 10H, Ph),
7.41-7.32 (m, 3H, Ph), 7.07 (br, 2H, Ph), 6.30 (d, 1H, J ) 1.0
Hz, Cp′), 5.82-5.76 (m, 2H, H6 and Cp′), 5.33-5.22 (m, 1H,
OCH2), 4.49 (ddt, 1H, J ) 11.7, 5.6, 2.2 Hz, OCH2), 3.53-3.36
(m, 3H, PCH2 and H1 or H4), 3.32 (s, 1H, H1 or H4), 2.58 (s,
3H, CH3), 2.30 (d, 3H, J ) 1.5 Hz, CH3), -0.17 (dd, 1H, J )
16.1, 2.0 Hz, H2 or H3), -0.29 (ddd, 1H, J ) 15.9, 9.5, 2.2 Hz,
H2 or H3). 13C NMR (150 MHz): δ 166.3 (CdO), 134.3-127.9
(Ph), 111.2, 110.5, 106.3, 88.9 (J ) 5.0 Hz), 87.6, 86.0, 83.5,
59.7 (J ) 5.8 Hz, OCH2), 53.5 (J ) 4.1 Hz, C1 or C4), 53.3 (J )
4.1 Hz, C1 or C4), 23.2 (PCH2), 22.9 (Me on diene), 11.65
(Cp′Me). 31P NMR (160 MHz): δ 53.0. For minor product 6b-
II: 31P NMR (160 MHz): δ 51.5.
[(η5:η1-2-Me -4-P h C5H 2CO2CH 2CH 2P P h 2)R u (η4-CH 2d
CHCHdCHP h )][P F 6] (8b). IR (cm-1, KBr): 1731 (νCdO).
HRMS calcd for C37H34O2PRu (M - PF6-) 643.1340, found m/z
643.1332. 1H NMR (600 MHz): δ 7.70-7.34 (m, 15H, Ph), 7.02
(t, 1H, J ) 7.4 Hz, Ph), 6.68-6.64 (m, 3H, Ph, Cp′), 6.58 (dd,
1H, J ) 11.0, 5.2 Hz, H5 or H6), 6.40 (d, 2H, J ) 7.4 Hz, Ph),
5.81-5.76 (m, 2H, Cp′ and H5 or H6), 5.13 (ddd, 1H, J ) 23.9,
12.4, 7.4 Hz, OCH2), 4.39 (ddt, 1H, J ) 11.8, 5.0, 2.5 Hz, OCH2),
3.41-3.34 (m, 1H, PCH2), 3.28-3.22 (m, 2H, PCH2 and H1),
3.42-3.24 (m, 2H, PCH
2), 2.12 (d, 3H, J ) 2.2 Hz, Cp′Me),
1.77 (d, 3H, J ) 1.7, 6.1 Hz, Me on diene), 1.42 (s, 9H, But),