6
Synthesis and Catalytic Activity of (η -p-Cymene)(phosphane)ruthenium(II) Complexes
FULL PAPER
(
25 °C):
δ
ϭ
7.5, 7.3, 7.2, (br, aromatic rings); 5.0, 4.8
CH(CH ], 3.4, 1.6 (PTHF); 2.7 [CH CH(CH ], 521(m), 474 (w) cm
CH(CH Cl , 25 °C): (617.54): calcd. C 51.93, H 3.02, N 2.27 (calcd. values take into
]; 98, 87, 30.5, 22 (p-cymene); 71, 27 (PTHF)
def.), 779 (w), 748 (w), 728 (w), 692 (m), 656(w), 602 (w), 570 (m),
Ϫ1
[CH
3
C
6
H
4
3
)
2
3
C
6
H
4
3
)
2
.
26.7
C H18.5Br1.6Cl0.70NO2.05P1.4Ru0.35
] ppm. 13C{ H} NMR (CD
1
0
.9 [CH
3
C
6
H
4
3
)
2
2
2
δ ϭ 134, 129 [P(C
ppm. FTIR (KBr): ν˜ ϭ 3057 (m, CϪH str., arene), 2941 (m, CϪH
str., PTHF), 2864 (m, CϪH str., PTHF), 1588 (w), 1492 (m), 1480
6
H
5
)
2
account the 12% of oxidized phosphane sites); found C 50.8, H
2.95, N 2.35. TGA: Continuous loss of mass from 180 °C, with
maxima at 210 °C (7%), 490 (37%) and 780 (16%). Residue at 800
(
m), 1435 (s, CϭC str., p-cymene), 1376 (m), 1246 (vs, NϪP str.), °C: 40%. No T
g
was observed in the DSC thermogram up to 300
1212 (vs, NϪP str.), 1198 (vs, NϪP str.), 1172 (vs), 1117 (m), 1094
°C.
(
vs, PϪOC str.), 1016 (w), 935 (v, br, POC def.), 840 (w), 786 (m,
6
Ϫ1
{[NP(OC
6
H
4
PPh
2
)
2
]
0.1[NP(O
2
C
20
H
12)]0.9[RuCl(η -p-cymene)-
PNP def.), 752 (m), 717 (w), 696 (m), 609 (w), 524 (s, br) cm
1.8Ru0.8 (672,74): calcd. C 57.8, H 4.91; N
.08.; found C 56.9, H 4.38, N 2.18 (calcd. values include the 0.7
.
6
(
PF
0.061 g, 0.065 mmol) was added to
[NP(OC PPh 0.1[NP(O (1b) (0.50 g, 0.225
mmol of PPh groups) in THF (30 mL) and the resulting mixture
was refluxed for 48 h. Then the solvent was evaporated and the free
PPh was extracted with diethyl ether (3 ϫ 20 mL). The reddish
solid residue was dried under vacuum at room temperature for 6 h.
6
)]0.05
}
n
(5): The complex [RuCl(η -p-cymene)(PPh
3 2 6
) ][PF ]
C
2
32.4
H32.8Cl1.6NO2.7P
(
a
solution of
{
6
H
4
2
)
2
]
2 20 n
C H12)]0.9}
PTHF content). TGA: Continuous loss of mass from 180 °C, with
maxima at 260 °C (24%), 480 °C (23%), 720 °C (10%). Residue at
8
2
Ϫ1
00 °C: 43%. T
g
(DSC) ϭ 189 °C, ∆C
p
ϭ 0.139 J[gK]
.
3
6
{
[NP(OC PPh
6
H
4
2
[RuCl
2
(η -p-cymene)])
2
]0.1[NP(O
2
C
20
H12)]0.9}
n
3
1
1
Yield 0.50 g (95%). P{ H} NMR ([D
δ ϭ 24.4, 23.2 (m, C PPh Ru), Ϫ8.5 [v br, NϭP(O
P(OC PPh Ϫ148 (m, PF
6
]DMSO suspension, 25 °C):
12), Nϭ
) ppm. FT IR (KBr): ν˜ ϭ 3053
6
(3): The reddish complex 3 was prepared by stirring a solution of
{
0
[NP(OC
6
H
4
PPh
2
)
2
]
0.1[NP(O
groups) in CH
(0.0735 g, 0.24 mmol of Ru) at room
2
C
20
H
12)]0.9
}
n
(1b)
(0.50 g,
6
H
4
2
2 20
C H
Ϫ
6
H
4
2
)
2
]
,
.225 mmol of PPh
2
2 2
Cl (30 mL) with the dimer
6
(m, CϪH str., arenes), 2965 (m, CϪH str, p-cymene), 2855 (w,
CϪH str., p-cymene), 1620 (w), 1591 (m), 1506 (w), 1436 (m), 1398
m), 1362 (m), 1317 (s), 1258 (sh,s, NϪP str.), 1218 (vs, NϪP str.),
1186 (sh,vs, NϪP str.), 1148 (sh, s), 1116 (m), 1069 (m, PϪOC str.),
61 (s, br, POC def.), 943 (sh, s), 895 (m), 865 (s), 838 (m, PϪF
str., PF6 ), 808 (s, PNP def.), 772 (w), 745 (s), 712 (m), 693 (s), 654
), 538 (m), 486 (m), 472 (m),
50 (m) cm . C22.1H14.3Cl0.05F0.3NO2.02P1.25Ru0.05 (377.42): calcd.
[Ru(η -p-cymene)Cl(µ-Cl)]
2
temperature for 5.5 h. The polymer was isolated according to the
(
procedure described previously for 2a. The yield was 0.51 g (90%).
3
1
1
P{ H} NMR (CD
PPh Ru), Ϫ2.8 [m, NϭP(O
P(OC PPh
aromatic rings); 5.0 [v br, CH
CH CH(CH ], 0.9 [v br, CH
C{ H} NMR (CD Cl , 25 °C): δ ϭ 149, (NPOC naphthalene
ring), 136, 134, 130, 124 (v, br naphthalene and phosphane ring),
2, 24 (br, p-cymene) ppm. FTIR (KBr): ν˜ ϭ 3054 (m, CϪH str.,
2
Cl
2
, 25 °C): δ ϭ 26.8 (m, Ph
2
PϭO), 23.0 (m,
9
C
6
H
4
2
2
C
20
H
12)], Ϫ23.5 [m, Nϭ
Ϫ
1
6
H
4
) ] ppm. H NMR (CD Cl , 25 °C): δ ϭ 7.3 (v br,
2 2 2 2
Ϫ
(
m), 571 (s), 560 (sh,m, PϪF str., PF
6
3
C
6
H
4
CH(CH
3
)
2
], 2.6 [v br,
ppm.
Ϫ1
4
3
C
6
H
4
3
)
2
3
C
6
H
4
CH(CH ) ]
3 2
1
3
1
C 70.3, H 3.82, Cl, F 1.98, N 3.71, P 10.3, Ru 1.34 (calcd. values
take into account the 20% of oxidized phosphane sites); found C
7.0, H 3.81, Cl, F 1.53, N 3.52, P 8.83, Ru 1.11. TGA: Continuous
2
2
6
3
loss of mass from 60 °C, with maxima at 510 °C (42.6%). Residue
arenes), 2960 (m, CϪH str., p-cymene), 2866 (m, CϪH str., p-cy-
mene), 1620 (w), 1592 (m), 1508 (m), 1465 (w), 1434 (m), 1398 (m),
1
at 800 °C: 57.4%. No T
to 300 °C.
g
was observed in the DSC thermogram up
363 (m), 1317 (s), 1256 (sh, s, NϪP str.), 1219 (vs, NϪP str.), 1190
(
1
7
sh, vs, NϪP str.), 1154 (sh, m), 1095 (w), 1072 (s, PϪOC str.),
030 (w), 963 (vs, br, POC def.), 895 (m), 868 (s), 811(s, PNP def.),
6
{
(
(
{
[NP(OC
PF
0.074 g, 0.079 mmol) was added to
[NP(OC PPh 0.2[NP(O
mmol of PPh groups) in THF (30 mL) and the resulting mixture
was refluxed for 57 h. Then the solvent was evaporated and the free
PPh was extracted with diethyl ether (5 ϫ 20 mL). The green solid
residue was dried under vacuum at room temperature for 12 h.
6
H
4
PPh
2
)
2
]
0.2[NP(O
2
C
20
H
10Br
2
)]0.8[RuCl(η -p-cymene)-
6
6
)]0.08
}
n
(6): The complex [RuCl(η -p-cymene)(PPh
solution of
(1c) (0.50 g, 0.345
3 2 6
) ][PF ]
72 (w), 746 (s), 713 (m), 694 (m), 655(m), 571 (s), 523 (m), 487
a
Ϫ1
(m) cm . C23.2H15.84Cl0.32NO2.04P1.2Ru0.16 (405.94): calcd. C 68.6,
6
H
4
2
)
2
]
2 20 2 n
C H10Br )]0.8}
H 3.93, N 3.45 (calcd. values take into account the 20% of oxidized
phosphane sites); found C 66.3, H 4.01, N 3.42. TGA: Continuous
loss of mass from 180 °C, with maxima at 212 (6%), 500 (31%) and
2
3
7
90 °C (7%). Residue at 800 °C: 56%. No T
g
was observed in the
DSC thermogram up to 300 °C.
3
1
1
Yield 0.50 g (94%). P{ H} NMR (CDCl
4 (m, C PPh Ru), Ϫ 9.3 [v br, NϭP(O
P(OC PPh
FT IR (KBr): ν˜ ϭ 3053 (m, CϪH str., arenes),
960 (m, CϪH str., p-cymene), 2852 (m, CϪH str., p-cymene), 1584
m), 1492 (m), 1437 (m), 1393 (m), 1354 (m), 1317 (s), 1258 (s,
NϪP str.), 1216 (vs, NϪP str.), 1187 (sh,vs, NϪP str.), 1115 (s),
065 (s, PϪOC str.), 956 (s, br, POC def.), 942 (vs), 872 (s), 838
3
suspension, 25 °C): δ ϭ
2
6
H
4
2
2 20 2
C H10Br
), Nϭ
6
{
Br
0
{
0
[NP(OC
6
H
4
PPh
2
[RuCl
2
(η -p-cymene)])
2
]
0.2[NP(O
2
C
20
H
10
-
6
6
H
4
2 2 .
) ]
2
)]0.8
}
n
(4): The dimer [Ru(η -p-cymene)Cl(µ-Cl)]
.31 mmol of Ru) was added to solution of
[NP(OC PPh 0.2[NP(O (1c) (0.50 g,
.345 mmol of PPh groups) in CH (30 mL), and the mixture
2
(0.095 g,
2
(
a
6
H
4
2
)
2
]
2 20 2 n
C H10Br )]0.8}
2
2 2
Cl
1
(
7
5
05
P
(
was stirred at room temperature for 5.5 h. The resulting solution
was concentrated to ca. 1 mL and poured dropwise into hexane
Ϫ
6
sh, PϪF str., PF ), 826 (s), 805 (s, PNP def.), 777 (s), 748 (m),
26 (s), 690 (s), 654 (m), 601 (m), 568 (s), 560 (sh, PϪF str., PF ),
6
Ϫ
(
500 mL) to give 4 as an orange solid that was dried in vacuo.
Subsequently, the product was reprecipitated from CH Cl /diethyl
ether, washed with Et O (2 ϫ 30 mL) and dried under vacuum at
room temperature for 1 d. Yield 0.53 g (88%). 31P{ H} NMR (25
C): δ ϭ 27.5 (m, Ph PϭO), 23.1 (m, C PPh Ru), Ϫ4.3 [m, Nϭ
)], Ϫ20.0 [m, NϭP(OC PPh
7.3 (v br, aromatic rings); 1.8 [br,
], 1.3 [br, CH CH(CH ] ppm. FTIR
KBr): ν˜ ϭ 3055 (m, CϪH str., arenes), 2958 (w, CϪH str., p-
cymene), 2865 (w, CϪH str, p-cymene), 1585 (m), 1493 (m), 1436
w), 1354 (m), 1317 (s), 1253 (sh, s, NϪP str.), 1218 (vs, NϪP str.),
Ϫ1
33 (s), 514 (s), 492 (s), 472 (s) cm . C24
1.48Ru0.08 (543.63): calcd. C 53.0, H 2.73, N 2.58, P 8.43; Ru 1.49
calcd. values take into account the 12% oxidized phosphane sites);
H14.72Br1.6Cl0.08F0.48NO2.-
2
2
2
1
found C 51.5, H 2.74, N 2.54, P 7.34, Ru 1.35. TGA: Continuous
loss of mass from 160 °C, with maxima at 220 °C (9%), 470 °C
40%), and 770 °C (9%). Residue at 800 °C: 39%. No T was ob-
g
°
2
6
H
4
2
1
P(O
25 °C):
CH
2
C
20
H10Br
2
6
H
4
2 2 .
) ] ppm H NMR
(
(
δ
ϭ
served in the DSC thermogram up to 300 °C.
3
C
6
H
4
CH(CH
3
)
2
3
C
6
H
4
3 2
)
(
Acknowledgments
(
1191 (sh, s, NϪP str.), 1154 (s), 1117 (w), 1066 (m, PϪOC str.),
The authors thank the Ministerio de Ciencia y Tecnolog ´ı a (Projects
959 (vs, br, POC def.), 943 (sh, s), 874 (m), 826 (m), 808 (m, PNP BQU-2001-3676, BQU2000-0227 and CAJAL-01-03), the FICYT
Eur. J. Inorg. Chem. 2004, 3668Ϫ3674
www.eurjic.org
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3673