4058 Organometallics, Vol. 19, No. 20, 2000
Komiya et al.
The following complexes were prepared by procedure A
except for 4a ,b. The amount of reactants used, yields, and
analytical and spectroscopic data are summarized in Table 4
or below.
4-CHd), 78.6 (s, 2- or 3-CHd), 79.6 (s, 3- or 2-CHd), 115.3 (d,
J ) 5 Hz, 6-CHd), 138.9 (brs, 5-CHd).
Ch a r a cter iza tion of Ru H(η5-C8H9)L2 (5). The following
(hydrido)ruthenium complexes RuH(η5-C8H9)L2 (5) were char-
1
[L ) P Me3 (4a )]. Complex 2 (15.2 mg, 0.0482 mmol) was
placed into an NMR tube, and then C6D6 (500 µL), PMe3 (20
µL, 0.19 mmol), and PPh3 as an internal standard were added.
The NMR tube was mechanically stirred at room temperature,
acterized by H and 31P{1H} NMR spectra, homo-decoupling,
and 2D-NMR measurements at low temperature, since they
were obtained as an equilibrium mixture with 4. They con-
tained several isomers, and the complete assignment of the
minor species was not feasible. Thus, only 31P{1H} NMR data
and the hydride signals for the minor species are described.
1
and the H and 31P{1H} NMR specta were measured periodi-
cally. After 24 h, complex Ru(η4-C8H10)(PMe3)3 (4a ) was formed
in 54% yield with concomitant formation of 3a in 10% yield.
These yields did not vary during the following 150 h. Further
reaction at 50 °C for an additional 96 h led to 4a and 3a in 4
and 84% yields, respectively. Complex 4a was characterized
spectroscopically in a mixture of 4a and 3a . Selected NMR
data: 1H NMR (300 MHz, C6D6): δ 4.51 (m, 2H, 2- and
3-CHd), 5.21 (m, 1H, 6-CHd), 6.23 (t, J ) 9.0 Hz, 1H, 5-CHd
), and other signals were obscured due to overlapping with
3a . 31P{1H} NMR (121.5 MHz, C6D6): δ -3.7 (dd, J ) 27, 8
Hz, 1P), 0.0 (dd, J ) 11. 8 Hz, 1P),1.0 (dd, J ) 27 11 Hz, 1P).
[L ) P Et3 (5c)]. Major species (5c-1): 1H NMR (300.4
MHz, -50 °C, CD3C6D5): δ -14.1 (t, J ) 26.9 Hz, 1H, Ru-H),
0.97 (dt, J ) 15.6, 7.2 Hz, 18H, PCH2CH3), 1.61 (sept, J ) 7.2
Hz, 6H, PCH2CH3), 3.20 (m, 3H, 2-CHd), 3.57 (brs, 1H,
5-CHd), 3.88 (brs, 1H, 1-CHd), 4.39 (t, J ) 7.5 Hz, 1H, 3-CHd
), 5.50 (brd, J ) 7.5 Hz, 1H, 7-CHd), 5.79 (dt, J ) 7.5, 4.2 Hz,
1H, 6-CHd). 31P{1H} NMR (121.6 MHz, -70 °C, CD3C6D5): δ
30.0 (d, J ) 15 Hz, 1P), 34.4 (d, J ) 15 Hz, 1P). Minor species
(5c-2): 1H NMR (300.4 MHz, -60 °C, CD3C6D5): δ -11.7 (dd,
J ) 33.0, 26.4 Hz, Ru-H). 31P{1H} NMR (121.6 MHz, -70 °C,
CD3C6D5): δ 28.4 (d, J ) 24 Hz, 1P), 46.8 (d, J ) 24 Hz, 1P).
Minor species (5c-3): 1H NMR (300.4 MHz, -70 °C,
CD3C6D5): δ -10.9 (t, J ) 27.6 Hz, Ru-H). 31P{1H} NMR (121.6
MHz, -70 °C, CD3C6D5): δ 30.3 (d, J ) 24 Hz, 1P), 46.6
(obscured by overlapping with a signal due to 5c-2). Minor
species (5c-4): 1H NMR (300.4 MHz, -60 °C, CD3C6D5): δ
-11.4 (dd, J ) 34, 26 Hz, Ru-H). The 31P{1H} NMR spectrum
was obscured. The ratio among 5c-1, 5c-2, 5c-3, and 5c-4
based on the integration of their hydride resonances was 1:0.5:
0.25:0.08, respectively.
[L ) P Me2P h (4b)]. Complex 2 (11.2 mg, 0.0355 mmol) was
placed in an NMR tube, and C6D6 (500 µL) and PMe2Ph (20
µL, 0.14 mmol) were introduced in this order. The NMR data
show slow formation of Ru(η4-C8H10)(PMe2Ph)3 (4b) at room
temperature for 24 h in 74% yield with concomitant formation
of 3b in 25% yield. Heating of the mixture at 50 °C for 24 h
led to the formation of 3b with the final distribution of 4b and
3b being 10 and 83% yield, respectively. Complex 4b was
characterized spectroscopically in a mixture of 4b and 3b.
Selected NMR data: 1H NMR (300.4 MHz, C6D6): δ 4.22-4.49
(m, 2H, 2- and 3-CHd), 5.12 (m, 1H, 6-CHd), 6.06 (t, J ) 9.0
Hz, 1H, 5-CHd). 31P{1H} NMR (121.5 MHz, C6D6): δ 5.75 (dd,
J ) 25, 5 Hz, 1P), 9.9 (dd, J ) 25, 7 Hz, 1P), 10.6 (dd, J ) 7,
5 Hz, 1P).
[L ) P Et2P h (5d )]. Major species (5d -1): 1H NMR (300.4
MHz, -20 °C, CD3C6D5): δ -14.18 (t, J ) 30 Hz, 1H, Ru-H),
0.6-1.0 (m, 12H, PCH2CH3), 1.93 (sext, J ) 7.5 Hz, 1H, PCH2-
CH3), 1.96 (sext, J ) 7.5 Hz, 1H, PCH2CH3), 2.21 (sext, J )
7.5 Hz, 2H, PCH2CH3), 2.29 (sext, J ) 7.5 Hz, 1H, PCH2CH3),
2.30 (sext, J ) 7.5 Hz, 1H, PCH2CH3), 2.51 (sext, J ) 7.5 Hz,
2H, PCH2CH3), 3.00 (m, 1H, 2-CHd), 3.65 (m, 1H, 4-CHd),
3.7 (m, 1H, 5-CHd), 3.95 (m, 1H, 1-CHd), 4.67 (t, J ) 7.5 Hz,
1H, 3-CHd), 5.43 (d, J ) 6.8 Hz, 1H, 7-CHd), 5.75 (dt, J )
6.8, 4.5 Hz, 1H, 6-CHd), 8-CH2 resonances (2H) were obscured
by the overlapping with PEt2Ph signals of 4d and 5d . 31P{1H}
NMR (121.5 MHz, -20 °C, CD3C6D5): δ 36.3 (d, J ) 15 Hz,
1P), 38.9 (d, J ) 15 Hz, 1P). Minor species (5d -2): 1H NMR
(300.4 MHz, -40 °C, CD3C6D5): δ -11.28 (dd, J ) 33.9, 24.0
Hz, Ru-H). 31P{1H} NMR (121.6 MHz, -60 °C, CD3C6D5): δ
36.3 (d, J ) 22 Hz, 1P), 48.0 (d, J ) 22 Hz, 1P). Minor species
(5d -3): 1H NMR (300.4 MHz, -40 °C, CD3C6D5): δ -10.53 (t,
[L ) P Et2P h (4d )]. 1 (178.6 mg, 0.567 mmol), diethylphen-
ylphosphine (395 µl, 2.27 mmol), and 4d (199.4 mg, 0.283
mmol) were used: yield 50%. Anal. Calcd for C38H55P3Ru: C,
64.66; H, 7.85. Found: C, 64.34; H, 8.06. IR (KBr, cm-1): 1636.
1H NMR (300 MHz, C6D6): δ 0.95 (dt, J ) 15.6, 7.2 Hz, 12 H,
PCH2CH3), 1.52 (q, J ) 7.3 Hz, 6H, PCH2CH3), 1.4-2.6 (m,
12H, PCH2CH3), 1.5-2.0 (m, 2H, 8-CH2), 1.8-2.4 (m, 2H,
7-CH2), 2.5-2.7 (m, 2H, 1- and 4-CHd), 4.46 (brs, 2H, 2- and
3-CHd), 5.41 (m, 1H, 6-CHd), 6.23 (t, J ) 9.3 Hz, 1H, 5-CHd),
6.75-7.50 (m, 15H, PPh). 31P{1H} NMR (121.5 MHz, rt,
C6D6): δ 22.4 (dd, J ) 24, 6 Hz, 1P), 27.8 (dd, J ) 24, 9 Hz,
1P), 31.2 (dd, J ) 9, 6 Hz, 1P). 13C{1H} NMR (74.5 MHz, rt,
C6D6): δ 9.26 (d, J ) 3 Hz, PCH2CH3), 9.39 (d, J ) 3 Hz,
PCH2CH3), 10.0 (d, J ) 4 Hz, PCH2CH3), 21.0 (s, 8-CH2), 24.2
(d, J ) 20 Hz, PCH2CH3), 24.9 (d, J ) 20 Hz, PCH2CH3), 27.6
(s, 7-CH2), 37.4 (dt, J ) 39, 4 Hz, 1-CHd), 43.2 (d, J ) 29 Hz,
4-CHd), 79.6 (s, 2- or 3-CHd), 81.1 (s, 3- or 2-CHd), 116.1
(brd, J ) 5 Hz, 6-CHd), 138.7 (brs, Ph).
J
) 29.1 Hz, Ru-H). 31P{1H} NMR (121.6 MHz -60 °C,
CD3C6D5): δ 47.2 (d, J ) 18 Hz). The corresponding phospho-
rus peak was obscured. The ratio among 5d -1, 5d -2, and 5d -3
based on the integration of their hydride species was 1:0.13:
0.06, respectively.
1
[L ) P (n -Bu )3 (5e)]. H NMR (300.4 MHz, 24 °C, C6D6): δ
[L ) P (n -Bu )3 (4e)]. 1 (168.1 mg, 0.534 mmol) P(n-Bu)3 (400
µl, 1.61 mmol) were used. 4e was obtained as an almost pure
yellow oil (403.2 mg, 0.495 mmol): yield 93%. This complex
was characterized spectroscopically. Selected NMR data: 1H
NMR (300 MHz, C6D6): δ 0.92 (t, J ) 7.2 Hz, 27H, PC3H6CH3),
1.2-2.1 (m, 54H, PC3H6CH3), 1.8-2.4 (8- and 7-CH2, over-
lapped with signals due PC3H6CH3), 2.46 (quint, J ) 6.3 Hz,
1H, 4-CHd), 2.60 (q, J ) 7.2 Hz, 1H, 1-CHd), 4.62 (brs, 1H,
3-CHd), 4.75 (m, 1H, 2-CH d), 5.26 (m, 1H, 6-CHd), 6.15 (t,
J ) 9.3 Hz, 1H, 5-CHd). 31P{1H} NMR (121.5 MHz, 24 °C,
C6D6): δ 9.5 (dd, J ) 25, 6 Hz, 1P), 13.1 (dd, J ) 25, 10 Hz,
1P), 18.1 (dd, J ) 10, 6 Hz, 1P). 13C{1H} NMR (74.5 MHz, rt,
C6D6): δ 14.1-14.3 (m, P(CH2)3CH3), 21.0 (s, 8-CH2), 25.1 (d,
J ) 10 Hz, PCH2(CH2)2CH3), 25.4 (d, J ) 10 Hz, PCH2(CH2)2-
CH3), 25.6 (d, J ) 10 Hz, PCH2(CH2)2CH3), 27.5-27.6 (m,
PCH2(CH2)2CH3), 31.1 (d, J ) 15 Hz, PCH2(CH2)2CH3), 31.6
(d, J ) 13 Hz, PCH2(CH2)2CH3), 33.1 (d, J ) 20 Hz, PCH2(CH2)2-
CH3), 36.6 (dt, J ) 39, 4 Hz, 1-CHd), 43.2 (brd, J ) 31 Hz,
-11.5 (t, J ) 32 Hz, 1H, Ru-H), 0.99 (t, J ) 7.5 Hz, 18H,
PC3H6CH3), other signals were obscured by significant over-
lapping with 4e. 31P{1H} NMR (121.6 MHz, 25 °C, C6D6): δ
23.6 (br, 1P), 27.6 (br, 1P).
Ru (η4-C8H8)(P Et3)3 (6) a n d Ru H(η4-C8H11)(P Et3)2 (7).
Triethylphosphine (160 µl, 1.09 mmol) was added to a solution
of 2 (82.3 mg, 0.261 mmol) in 2 mL of toluene. The reaction
mixture was stirred at 50 °C for 3 days. After removal of
volatile materials, the NMR spectrum of the residual red oil
shows a crude mixture of 6 and 7 in 1:1 ratio. Fractional
crystallization from pentane gave red crystals of 6 (18.7 mg,
0.0334 mmol): yield 13%. Heating of the isolated 4c in benzene
at 70 °C for 100 h also caused disproportionation reaction of
the η4-C8H10 moiety to give a mixture of Ru(η4-C8H8)(PEt3)3
(6) and RuH(η5-C8H11)(PEt3)3 (7) in 43 and 42% yields,
respectively. Complex 6 was characterized by X-ray analysis
and NMR spectrum. 1H NMR (300.4 MHz, 23 °C, C6D6): δ 0.88
Komiya, Sanshiro
