3750 Organometallics, Vol. 20, No. 17, 2001
Ta ble 6. Cr ysta l Da ta a n d Str u ctu r e Refin em en t Deta ils for Com p ou n d s 1-4
J azzar et al.
1
2
3
4
empirical formula
fw
C
57H49OP3Ru
C68.2H65.4O1.8P3Ru
1107.79
C45H38O2P2Ru
773.76
C48H50O3P2RuS2
902.01
943.93
T/K
170(2)
150(2)
150(2)
150(2)
cryst syst
space group
a/Å
b/Å
orthorhombic
Pbca
19.0110(5)
18.8250(4)
25.5770(7)
triclinic
P1h
monoclinic
P21/m
8.7830(6)
24.4420(8)
9.331(2)
triclinic
P1h
9.7870(1)
12.1770(2)
24.8940(4)
91.170(1)
94.572(1)
111.824(1)
2741.36(7)
2
9.3177(3)
12.5569(4)
20.0241(8)
97.525(2)
95.620(2)
110.911(2)
2143.05(13)
2
c/Å
R/deg
â/deg
114.977(7)
γ/deg
V/Å3
9153.5(4)
8
1.37
0.488
1815.8(4)
2
1.415
0.558
796
Z
Dc/g cm-3
1.342
0.420
1156
1.398
0.579
936
µ/mm-1
F(000)
3904
cryst size/mm
θ range for data collecn/deg
index ranges
0.20 × 0.20 × 0.03
3.05-23.82
-21 e h e 21
-21 e k e 20
-29 e l e 29
55 531
0.13 × 0.13 × 0.08
3.54-25.00
-11 e h e 11
-14 e k e 14
-29 e l e 29
36 392
0.25 × 0.20 × 0.06
3.66-27.69
0 e h e 11
-31 e k e 31
-12 e l e 11
24 744
0.20 × 0.10 × 0.10
3.61-24.98
0 e h e 11
-14 e k e 13
-23 e l e 23
15 221
no. of rflns collected
no. of indep rflns
7015 (R(int) ) 0.1551)
9605 (R(int) ) 0.0572)
4281 (R(int) ) 0.0966)
7186 (R(int) ) 0.1070)
no. of rflns obsd (>2σ(I))
no. of data/restraints/params
goodness-of-fit on F2
4947
8072
3306
5869
7015/0/560
0.984
9605/0/682
1.028
4281/0/249
1.017
7186/1/515
0.990
final R1, wR2 indices (I > 2σ(I))
final R1, wR2 indices (all data)
largest diff peak, hole/e Å-3
0.0672, 0.1552
0.1048, 0.1795
1.172, -0.552
0.0448, 0.1154
0.0578, 0.1249
1.302, -0.821
0.0467, 0.1029
0.0696, 0.1141
0.545, -0.938
0.0589, 0.1653
0.0736, 0.1825
0.910, -1.099
1
δ 8.00-6.60 (br, 45H, PC6H5), 1.79 (br s, 4H, C2H4). H NMR
(C6D5CD3, 400 MHz, 203 K): δ 2.34 (br s, 2H, C2H4), 1.33 (br
s, 2H, C2H4). 31P{1H} NMR (C6D6, 293 K): δ 48.4 (br s). 31P-
{1H} NMR (C6D5CD3, 203 K): δ 45.6 (t, J PP ) 9.7 Hz), 49.3 (d,
(s). 13C{1H} NMR (C6D6, 293 K): δ 208.2 (s, Ru-OdC), 204.9
(t, J CP ) 12.8 Hz, Ru-CO), 202.9 (t, J CP ) 14.9 Hz, Ru-C),
145.9 (s), 144.9 (s), 135.7 (t, J CP ) 20.2 Hz), 134.4 (t, J CP ) 5.9
Hz), 130.3 (s), 130.2 (s), 129.0 (s), 120.2 (s), 24.0 (s, CH3). IR
(cm-1): 1932 (νRuH), 1899 (νCO), 1583 (νRu-OdC).
J PP ) 9.7 Hz). 13C{1H} NMR (C6D6, 293 K): δ 214.1 (q, J CP
)
13.7 Hz, Ru-CO), 29.8 (s, C2H4). 13C{1H} NMR (C6D5CD3, 263
K): δ 213.4 (q, J CP ) 13.0 Hz, Ru-CO), 29.4 (br s, C2H4), 25.7
(s, C2H4). 13C{1H} NMR (C6D5CD3, 218 K): δ 213.3 (br t, J CP
) 20.1 Hz, Ru-CO), 30.0 (br s, C2H4), 28.6 (s, C2H4). IR (cm-1):
1854 (νCO).
Ru H(o-C6H4C(O)CH3)(DMSO)(P P h 3)2 (4). DMSO (29 µL,
0.40 mmol) was added to a toluene suspension (5 mL) of RuH-
(C6H4C(O)CH3)(PPh3)3 (0.2 g, 0.20 mmol). The mixture was
stirred for 30 min to give a homogeneous solution and then
concentrated to ca. 1 mL. Addition of hexane (5 mL) and
vigorous stirring for 5 min afforded a deep red oil. This
operation was repeated twice more to give 4, which was
isolated as a light red powder upon drying in vacuo (0.162 g,
98%). Recrystallization from toluene/hexane afforded red
needles suitable for X-ray diffraction. Anal. Found (calcd) for
Ru H(o-C6H4C(O)CH3)(P P h 3)3 (2). To a suspension of
RuH2(H2)(PPh3)3 (0.2 g, 0.22 mmol) in 5 mL of thf was added
an excess of acetophenone (366 µL, 3.1 mmol). The mixture
was warmed with stirring to 45 °C for 12 h. The solution was
concentrated to yield an orange precipitate, which was filtered
off, washed with hexane (3 × 10 mL), and dried in vacuo.
Yield: 0.183 g, 81%. Block-shaped orange crystals were formed
when thf solutions were left at room temperature for 2 weeks.
Anal. Found (calcd) for RuC62H53P3O.C4H4O: C, 72.8 (73.66);
1
RuC46H44P2O2S‚(CH3)2SO: C, 63.8 (63.91); H, 5.54 (5.62). H
NMR (C6D6, 400 MHz, 293 K): δ 7.80-6.90 (m, 30H, C6H5),
6.86 (br d, J HH ) 7.59 Hz, 1H, C6H4), 6.74 (br d, J HH ) 7.59
Hz, 1H, C6H4), 6.38 (br t, J HH ) 7.20 Hz, 1H, C6H4), 6.12 (br
t, J HH ) 6.80 Hz, 1H, C6H4), 2.09 (s, 6H, CH3) 1.67 (s, 3H,
CH3), -15.30 (t, J HP ) 24.58 Hz, 1H, Ru-H). 31P{1H} NMR
(C6D6, 293 K): δ 58.04 (s). 13C{1H} NMR (C6D6, 293 K): δ 206.4
(s, Ru-OdC), 195.2 (t, J CP ) 15.8 Hz, Ru-C), 146.2 (s), 145.3
(s), 136.6 (t, J CP ) 19.1 Hz), 133.8 (t, J CP ) 5.8 Hz), 129.9 (s),
129.2 (s), 128.9-127.5 (m), 118.8 (s), 54.6 (s, CH3), 23.7 (s,
CH3). IR (cm-1): 1971 (νRuH), 1571 (νRu-OdC).
1
H, 5.48 (5.34). H NMR (C6D6, 400 MHz, 293 K): δ 7.88-6.75
(m, 47H, PC6H5, o-C6H4), 6.30 (br t, J HH ) 7.19 Hz), 6.45 (br t,
J HH ) 7.19 Hz), 1.36 (s, 3H, CH3), -15.42 (dt, J HP ) 25.98 Hz,
J HP ) 13.19 Hz, 1H, Ru-H). 31P{1H} NMR (C6D6, 293 K): δ
57.0 (d, J PP ) 23.1 Hz), 46.6 (t, J PP ) 23.1 Hz). 13C{1H} NMR
(C6D6, 293 K): δ 196.3 (s, Ru-OdC), 146.7 (s), 146.4 (s),
135.3-133.9 (m), 132.8 (s), 132.3 (s), 132.2 (s), 131.6 (s), 129.8
(s), 129.7 (s), 118.8 (s), 23.2 (s, CH3). IR (cm-1): 1940 (νRuH),
1574 (νRu-OdC).
Ca ta lytic Rea ction s. A 50 mL, three-necked, round-bottom
flask equipped with an argon inlet, an outlet bubbler, and a
reflux condenser was flame-dried under vacuum and flushed
with argon. It was then charged with complexes 1-6 (0.04
mmol), 261 µL (2 mmol) of triethoxyvinylsilane, 420 µL (2
mmol) of 2′-methylacetophenone, 3 mL of toluene, and 200 µL
of dodecane as an internal reference. The solutions were stirred
and heated to 135 °C. Two hundred microliter aliquots of
solution were removed via syringe every 30 min over 4 h. The
aliquots were diluted with hexane and passed through a short
column of Celite to remove ruthenium residues. The formation
of 2′-methyl-6′-[2-(triethoxysilyl)ethyl]acetophenone (retention
time confirmed by an authentic sample) was analyzed by GC,
as follows: Fisons GC 8000 series (equipped with a Supelco
capillary column, 30 m × 0.32 mm) temperature program, 70
Ru H(o-C6H4C(O)CH3)(CO)(P P h 3)2 (3). A benzene suspen-
sion (10 mL) of RuH(o-C6H4C(O)CH3)(PPh3)3 (0.2 g, 0.20 mmol)
was stirred under 1 atm of carbon monoxide for 30 min, during
which time the color changed from red to yellow. The solution
was concentrated and hexane added (10 mL) to give a yellow
precipitate. This was filtered off, washed with 2 × 10 mL
hexane, and dried in vacuo. Yield: 0.12 g, 76%. Anal. Found
(calcd) for RuC45H38P2O2: C, 69.4 (69.85); H, 4.87 (4.95). 1H
NMR (C6D6, 400 MHz, 293 K): δ 7.60 (br, 10H, C6H5), 7.57
(br d, J HH ) 7.60, 1H, C6H4), 6.90 (br, 20H, C6H5), 6.88 (br d,
J HH ) 7.60, 1H, C6H4), 6.56 (br t, J HH ) 7.60, 1H, C6H4), 6.49
(br t, J HH ) 7.60, 1H, C6H4), 1.66 (s, 3H, CH3), -14.29 (t, J HP
) 21.18 Hz, 1H, Ru-H). 31P{1H} NMR (C6D6, 293 K): δ 55.29