was discarded by filtration after 30 minutes. CO was then bubbled
through the solution and the green solid, which precipitated, was
collected by filtration and dried in vacuum at room temperature.
Yield 0.61 g, 90%. It was characterised crystallographically and
After cooling, the autoclave was carefully depressurised, opened
and the contents from within and outside the glass liner combined.
They were analysed by GC (1-hexene as substrate) or C NMR
(2-propen-1-ol as substrate).
1
3
6
spectroscopically (Table 2) in comparison with the literature data.
Crystallography
Carbonylmethylbis(triisopropyl)phosphinerhodium(I)
i
[
RhCl(CO)(PBu
3
)
2
]. SMART diffractometer with graphite-
i
3
˚
[
RhCl(CO)(PPr
3
)
2
] (0.8 g, 1.7 mmol) in diethyl ether (5 cm ) was
monochromated Mo-Ka radiation (k = 0.71073 A), T =
3
◦
stirred with CH
under an atmosphere of argon. The solution was allowed to warm
to room temperature. The yellow solution was filtered from the
3
Li (1.3 cm , 1.4 M in diethyl ether) at −20 C
125 K. C25
H
54OClP
2
Rh, M = 570.98, monoclinic, space group
˚
−3
P2(1)/c, a = 9.3678(14), b = 12.7401(18) c = 13.0138(19) A, b =
◦
3
˚
101.414(2) , U = 1522.4(4) A , Z = 2, D
c
= 1.246 Mg m , l =
3
−1
precipitated LiCl. The LiCl was washed with diethyl ether (2 cm )
and filtered. To the combined filtrates, light petroleum (2 cm )
0.767 mm , F(000) = 608. Of 8950 measured data, 2776 were
3
unique (Rint = 0.0497) and 2227 observed (I > 2r(I)]) to give R =
1
◦
was added. The resulting solution was cooled to −110 C, then
0.0418 and wR
2
= 0.1132.
allowed to crystallise. The green solid was collected by filtration
and recrystallised from acetone. Yield 0.5 g, 65%. The complex
was characterised spectroscopically (Table 2).
i
[
RhCl(CO)(PPr
3
)
2
]. Rigaku Mercury/MM007 RA diffrac-
˚
tometer Mo-Ka radiation (k = 0.71073 A), confocal optics,
9
3 K. C19
H
42OClP
2
Rh, M = 486.83, monoclinic, space group
˚
−3
P2(1)/c, a = 8.0534(16), b = 8.875(2), c = 16.440(4) A b =
i
13
Reaction of [Rh(CH
3
)(CO)(PPr
3
)
2
] with CO
◦
3
˚
9
2.301(7) , U = 1174.1(5) A , Z = 2, D
c
= 1.377 Mg m , l =
−
1
i
0.982 mm , F(000) = 512. Of 6740 measured data, 2056 were
1
[Rh(CH
3
)(CO)(PBu
3
)
2
] (0.02 g) was dissolved in d -thf in an
8
unique (Rint = 0.0532) and 1665 observed (I > 2r(I)]) to give R
0.0374 and wR
=
NMR tube. Carbon monoxide was bubbled through the solu-
3
1
1
13
◦
2
= 0.1098. All data were corrected for Lorentz, po-
tion for 2–5 minutes. P, H and C NMR data at −50
C
larisation and long-term intensity fluctuations. Absorption effects
were corrected on the basis of multiple equivalent reflections or by
semi-empirical methods. Structures were solved by direct methods
indicated the production of the monophosphine compound:
1
3
13
i
[
Rh( COCH
3
)( CO)
3
(PPr )].
3
2
9
and refined by full-matrix least-squares against F (SHELXTL).
All hydrogen atoms were assigned riding isotropic displacement
parameters and constrained to idealised geometries.
1
3
13
i
Reaction of [Rh( COCH
3
)( CO)
3
(PPr
3
)] with CD OD
3
3
13
CD
3
OD (∼0.5 cm ) was added to a solution of [Rh( COCH
3
13
)-
C
1
3
i
31
1
(
CO)
3
(PPr
3
)] in d
8
-thf in an NMR tube. The P, H and
◦
NMR spectra were recorded at −50 C indicating the formation
Acknowledgements
1
3
13
i
of the compound [Rh( C(CH
3
)O · · · DOCD
3
)( CO)
3
(PPr
3
)].
We thank Lyondell Chemical Company (P. C., D. F. S. W.) for
studentships in support of this work.
1
3
13
i
Action of argon on [Rh( C(CH
3
)O · · · DOCD
3
)( CO)
3
(PPr
3
)]
In an NMR tube, argon was passed through the so-
References
1
3
13
i
lution of [Rh( C(CH
3
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(PPr
3
)] in d
8
-thf
H
3
1
1
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1
3
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2
C. D. Frohning and C. W. Kohlpaintner, in Applied Homogeneous
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3
13
i
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3
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i
+
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3
3
3
4
5
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(
[
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1
3
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994, 620, 1157.
7
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3
propen-1-ol (1 cm ) was added, followed by the required phosphine
−
4
8 L. Porri, A. Lionetti, G. Allegra and A. Immirzi, Chem. Commun., 1965,
(
(
2 × 10 mol). The solution was transferred into a preflushed
3
36.
argon) autoclave containing a glass liner, which was pressurized
with CO/H
9
G. M. Sheldrick, SHELXTL Version 6.10, Bruker AXS, Madison WI,
2004.
◦
2
(2:1) sealed and heated for 2.5 h at 125 C by a heater.
2
394 | Dalton Trans., 2008, 2389–2394
This journal is © The Royal Society of Chemistry 2008