5744
D.P. Allen et al. / Journal of Organometallic Chemistry 690 (2005) 5736–5746
then dried under vacuum overnight to yield a light yel-
low solid (302 mg, 99%). X-ray quality crystals were ob-
tained via slow vapour diffusion of hexane into a THF
solution of the rhodium complex.
(102.36 mg, 0.263 mmol) and dissolved in dry, deoxy-
genated toluene (7 ml). In a separate vial, P(2-furyl)3
(242.46 mg, 1.04 mmol) was diluted with toluene
(3 ml). The phosphine solution was then added to the
schlenk flask containing the rhodium complex and this
was stirred for 30 min. At this stage, the rhodium/phos-
phine solution was gravity filtered into a 50 ml schlenk
flask containing an IMes (156 mg, 0.512 mmol) solution
in toluene (3 ml). A further 2 ml of toluene was used to
rinse the filter paper. This mixture was then stirred for
16 h. At this stage, the sealed schlenk flask was removed
from the glovebox and placed on the schlenk line where
the solution was concentrated to a volume of approxi-
mately 2 ml. Then dry, deoxygenated hexane (15 ml)
was added to precipitate a fine yellow solid. This mix-
ture was cooled at ꢀ20 ꢁC for 2 h, and then filtered
using a schlenk apparatus. The solid was washed with
hexane (3 · 10 ml) and then dried under vacuum over-
night to yield a light yellow solid (442.83 mg, 93%).
X-ray quality crystals were obtained via slow vapour
diffusion of hexane into a THF solution of the rhodium
complex.
1
H NMR (400 MHz, C D ), d:
6
6
1
.92 (s, 6H), 2.42 (s, 6H), 2.91 (s, 6H), 3.26 (s, 9H),
3
7
.29 (s, 9H), 6.37 (s, 2H), 6.57 (m,12H), 6.91 (s, 2H),
.15 (s, 2H), 7.75–7.25 (br, 12H)
13
C NMR (600 MHz, C D ), d:
6
6
2
0.29, 21.42, 22.39, 54.61, 54.67, 112.39, 112.50, 112.59,
1
1
22.93, 127.95, 128.67,130.02, 130.43, 135.81, 136.70 (m),
37.45, 137.62 (d, J = 11.2 Hz), 138.74, 139.32,160.01
(
d, J = 44 Hz), 191.5 (ddd, J = 117, 49, 14 Hz)
31
P NMR (400 MHz, d -toluene), d:
8
4
4.95 (dd, J
= 207 Hz, J
= 40 Hz), 32.60 (dd,
PꢀRh
PꢀP
J
= 121 Hz, J
= 40 Hz)
PꢀRh
MS (m/z)
PꢀP
+
[
M ꢀ Cl] = 1111.3058,
1112.3114,
1113.3079,
1
1
114.3009 (calculated isotope distribution = 1111.4,
112.4, 1113.4, 1114.4).
4
.4. Preparation of [(IMes)Rh(P(p-F-Ph) ) Cl] (8d)
2
3
1
H NMR (500 MHz, C D ), d:
6
6
An oven dried 50 ml schlenk flask with stir bar was
taken into the glovebox, and was charged with [Rh(P(p-
2.01 (s, 6H), 2.23 (s, 6H), 2.82 (s, 6H), 5.89 (m, 3H),
5.98 (m, 3H), 6.43 (s, 2H), 6.59 (br, 3H), 6.79 (br, 5H),
6.95 (br, 2H) 6.99 (m, 6H)
F-Ph) ) Cl] (251 mg, 0.231 mmol). Then IMes (76 mg,
3
3
1
3
0
.250 mmol) was added to the schlenk flask. Then dry,
C NMR (500 MHz, C D ), d:
6 6
deoxygenated toluene (15 ml) was added and the light or-
ange mixture turned homogeneous and gradually light-
ened to a pale yellow solution after stirring for 16 h. At
this stage, the sealed schlenk flask was removed from
the glovebox and placed on the schlenk line where the
solution was concentrated to a volume of approximately
19.5, 21.4, 22.0, 110.6 (d, J = 6.8 Hz), 111.1 (d,
J = 7.2 Hz), 122.5 (d, J = 20.6 Hz),123.4, 123.6 (d,
J = 19.2 Hz), 129.2, 130.2, 135.7, 137.9, 138.4, 139.2,
145.4 (d, J = 4.2 Hz), 146.0 (d, J = 3.9 Hz), 148.8 (d,
J = 56.7 Hz), 151.0 (d, J = 56.6 Hz)
3
1
P NMR (500 MHz, C D ), d:
6
6
2
ml. Then dry, deoxygenated hexane (15 ml) was added
ꢀ8.6 (dd, J
= 206 Hz, J
= 44 Hz), 7.8 ppm,
PꢀP
PꢀRh
to precipitate a fine, light yellow solid. This mixture was
cooled at ꢀ20 ꢁC for 2 h, and then filtered using a schlenk
apparatus. The solid was washed with hexane (3 · 10 ml)
and then dried under vacuum overnight to yield a light
yellow solid (243 mg, 98%).
(dd, J
= 123 Hz, J
= 44 Hz).
PꢀP
PꢀRh
4.6. Preparation of [(IMes)Rh(P(OPh) ) Cl] (8f)
3
2
Route 1: an oven dried 50 ml schlenk flask with stir bar
was taken into the glovebox and charged with
[Rh(P(OPh) ) Cl] (148 mg, 0.139 mmol). Then, IMes
1
H NMR (400 MHz, C D ), d:
6
6
1
.58 (s, 6H), 2.32 (s, 6H), 2.70 (s, 6H), 6.23, (s, 2H),
3
3
6
1
.54 (m, 12H), 6.69 (s, 2H), 7.01 (s, 2H), 7.45–7.02 (br,
2H)
(46.0 mg, 0.150 mmol) was weighed and added to the
schlenk flask. Then dry, deoxygenated toluene (10 ml)
was added and the yellow mixture turned homogeneous
and gradually lightened to a very pale yellow solution
after stirring for 16 h. At this stage, the sealed schlenk
flask was removed from the glovebox and placed on the
schlenk line where the solution was concentrated to a vol-
ume of approximately 1 ml. Then dry, deoxygenated hex-
ane (8 ml) was added to precipitate a fine, light yellow
solid. This mixture was cooled at ꢀ20 ꢁC for 2 h, and then
filtered using a schlenk apparatus. The solid was washed
with hexane (3 · 5 ml) and then dried under vacuum over-
night to yield a light yellow solid (75.6 mg, 52%).
13
C NMR (400 MHz, C D ), d:
6
6
2
0.14, 21.51, 22.20, 114.42 (m), 123.46, 128.93,
1
1
30.34, 133.21, 133.60, 135.73, 137.08 (br), 138.06 (m),
38.33, 138.44, 139.31, 162.45 (d, J = 29 Hz), 164.95
(
d, J = 30 Hz), 188.50 (ddd, J = 117, 49, 14 Hz)
31
P NMR (400 MHz, d -toluene), d:
8
4
6.24 (dd, J
= 208 Hz, J
= 39 Hz).
PꢀP
= 39 Hz), 33.66 (dd,
PꢀP
PꢀRh
J
4
= 121 Hz, J
PꢀRh
.5. Preparation of [(IMes)Rh(P(2-furyl) ) Cl] (8e)
3
2
An oven dried 50 ml schlenk flask with stir bar was
taken into the glovebox, charged with [Rh(C H ) Cl]
Route 2: an oven dried 50 ml schlenk flask with stir
bar was taken into the glovebox. [Rh(C H ) Cl]
2
2
4 2
2
2
4 2