Solid-gas carbonylation of aryloxide rhodium(I) complexes: Stepwise reaction forming Vaska-type complexes

Article abstract of DOI:10.1016/j.ica.2004.02.030

Aryloxide rhodium(I) complexes Rh(OAr)(PPh₃)₃ (1a: Ar=C₆Cl₅, 1b: Ar=C₆F₅, 1c: Ar=C ₆H₄-NO₂-4) react with CO in toluene solutions to produce Vaska-type complexes trans-Rh(OAr)(CO)(PPh₃)₂ (2a: Ar=C₆Cl₅, 2b: Ar=C₆F₅, 2c: Ar=C₆H₄-NO₂-4). Carbonylation of a similar complex with PMe₃ ligands, Rh(OC₆H₄-NO ₂-4)(PMe₃)₃ (3c), also forms trans-Rh(OC ₆H₄-NO₂-4)(CO)(PMe₃)₂ (4c). Molecular structures of the complexes are determined by X-ray crystallography and NMR spectroscopy. Complex 1a reacts with CO in the absence of solvent to produce a mixture of 2a and complex A, the latter of which shows the IR and ¹³C{¹H} signals due to the carbonyl ligand at different positions from those of 2a. Addition of Et₂O to the above mixture turns it into analytically pure 2a. Carbonylation of 1b and 1c under the solvent-free conditions produces complexes B and C as the respective products of the solid-gas reaction. Recrystallization of B and C turns them into 2b and 2c, respectively. Complex 3c also reacts with CO in the solid state to form a mixture of 4c and complex D, although the latter complex is converted slowly into 4c even in the solid state.

Full text of DOI:10.1016/j.ica.2004.02.030

Inorganica Chimica Acta 357 (2004) 3007–3013
www.elsevier.com/locate/ica
Solid–gas carbonylation of aryloxide rhodium(I) complexes:
stepwise reaction forming Vaska-type complexes
*
Kohtaro Osakada , Hidetake Ishii
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan
Received 6 February 2004; accepted 14 February 2004
Available online 10 June 2004
Abstract
Aryloxide rhodium(I) complexes Rh(OAr)(PPh3)3 (1a: Ar ¼ C6Cl5, 1b: Ar ¼ C6F5, 1c: Ar ¼ C6H4–NO2-4) react with CO in toluene
solutions to produce Vaska-type complexes trans-Rh(OAr)(CO)(PPh3)2 (2a: Ar ¼ C6Cl5, 2b: Ar ¼ C6F5, 2c: Ar ¼ C6H4–NO2-4).
Carbonylation of a similar complex with PMe3 ligands, Rh(OC6H4–NO2-4)(PMe3)3 (3c), also forms trans-Rh(OC6H4–NO2-
4)(CO)(PMe3)2 (4c). Molecular structures of the complexes are determined by X-ray crystallography and NMR spectroscopy.
Complex 1a reacts with CO in the absence of solvent to produce a mixture of 2a and complex A, the latter of which shows the IR and
13C{1H} signals due to the carbonyl ligand at different positions from those of 2a. Addition of Et2O to the above mixture turns it into
analytically pure 2a. Carbonylation of 1b and 1c under the solvent-free conditions produces complexes B and C as the respective
products of the solid–gas reaction. Recrystallization of B and C turns them into 2b and 2c, respectively. Complex 3c also reacts with CO
in the solid state to form a mixture of 4c and complex D, although the latter complex is converted slowly into 4c even in the solid state.
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Carbon monoxide; Rhodium; Carbonyl complex; Solid phases reaction
1. Introduction
than dissociative pathways in many cases because pre-
dissociation of the ligand in solution is accelerated by
weak coordination of a solvent molecule to the vacant
site. The intermediate complexes of the solid–gas reac-
tions may have different structures from those in solu-
tion, and their structures and properties are of a
significant interest.
In this paper, we report the reaction of CO with
aryloxide rhodium(I) complexes with tertiary phosphine
ligands, Rh(OAr)(PPh3)3 and Rh(OAr)(PMe3)3, in the
absence of solvent. The products differ from those of the
carbonylation in solution, Rh(OAr)(CO)(PR3)2, but
they are easily converted into the Vaska-type complexes
upon treatment with solvents. Reaction profiles, moni-
tored by IR spectroscopy and the CP/MAS 13C NMR
spectra of the products are also presented.
Reactions of small molecules such as H2, acetylene
and ethylene with the complexes of late transition metals
are well known to cause coordination of these small
molecules and activation of their bonds by the transition
metal centers. Most of the reactions are carried out after
dissolving the complexes in a solvent in order to make
contact of the complex with gaseous compound smooth.
A few papers reported the solid–gas reactions of tran-
sition metal complexes with small molecules [1–4]. These
results suggest that the small molecules penetrate within
the crystals or microcrystals of the solid complexes
rapidly. Reactions of transition metal complexes in so-
lutions are often triggered by dissociation of auxiliary
ligands such as tertiary phosphines. The solid–gas re-
actions of a small molecule with transition metal com-
plex are considered to proceed via the pathways other
2. Results and discussion
* Corresponding author. Tel.: +81-45-924-5222; fax: +81-45-924-
5276.
E-mail address: kosakada@res.titech.ac.jp (K. Osakada).
Aryloxide rhodium complexes, Rh(OAr)(PPh3)3 (1a:
Ar ¼ C6Cl5, 1b: Ar ¼ C6F5, 1c: Ar ¼ C6H4–NO2-4), were
0020-1693/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2004.02.030

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K. Osakada, H. Ishii / Inorganica Chimica Acta 357 (2004) 3007–3013
prepared from the reaction of PPh3 with [Rh(l-
OAr)(cod)]2, and were characterized by NMR spec-
troscopy and elemental analyses (Eq. (1)).
Ar
PPh
Rh
3
1
2
O
Rh
+
Ph P
3
OAr
3 PPh
3
2
– cod
PPh
3
1a : Ar = C Cl ,
6
5
1b : Ar = C F ,
6
5
1c : Ar = C H -NO -4
6
4
2
ð1Þ
The 31P{1H} NMR spectra of the complexes exhibit a
doublet of triplets and a doublet of doublets in a 1:2
peak area ratio. These peaks are assigned to the P nu-
cleus at trans position of the aryloxide ligand and those
at cis positions, respectively. The reactions of
PPh3
Rh
PPh3
Rh
OC
OAr
PPh3
Ph3P
OAr
PPh3
+ CO
– PPh3
1a : Ar = C6Cl5,
1b : Ar = C6F5,
1c : Ar = C6H4-NO2-4
2a : Ar = C6Cl5,
Fig. 1. ORTEP drawings of (a) 2a, (b) 2b, (c) 2c, and (d) 4c at 50%
ellipsoidal levels. Hydrogen atoms were omitted.
2b : Ar = C6F5,
2c : Ar = C6H4-NO2-4
ð2Þ
CO with complexes 1a–1c in toluene solution proceed
smoothly at room temperature to afford Vaska-type
complexes, trans-Rh(OAr)(CO)(PPh3)2 (2a: Ar ¼ C6Cl5,
2b: Ar ¼ C6F5, 2c: Ar ¼ C6H4–NO2-4), via substitution
of a PPh3 ligand with CO, as shown in Eq. (2). IR
spectra of 2a–2c exhibit the bands due to CO stretching
at 1979, 1987 and 1985 cmꢀ1, respectively. Complex 2a-
13CO containing 13CO labeled carbonyl ligand was
prepared from the reaction of 13CO with 1a, and showed
the 13C{1H} NMR peak of the carbonyl carbon at d
190.07, which is accompanied by splitting due to Rh–C
and P–C coupling ()70 °C). 13C{1H} NMR spectra of
2b-13C and 2c-13C at room temperature exhibit the sig-
nals at d 189.93 and 189.60, respectively, although
broadening of the signal prevents from determination of
precise P–C coupling constants. These IR and NMR
peak positions are in the range of already reported
Vaska type complexes. Complex Rh(OC6H4–NO2-
4)(PMe3)3 (3c), prepared from the reaction of PMe3 with
[Rh(l-OC6H4–NO2-4)(cod)]2, also reacts with CO in
toluene to afford the carbonyl complex, trans-
Rh(OC6H4–NO2-4)(CO)(PMe3)2 (4c) (Eq. (3)).
distances and angles are listed in Table 1. Rh–O–C bond
angles (126–135°) and O–C bond distances (1.28–1.31
A) are similar to those of the reported alkoxide and
ꢀ
aryloxide complexes of late transition metals [5–9].
Solid–gas carbonylation of 1a was conducted by in-
troducing CO (1 atm) into a Schlenk flask containing the
complex. Color of the solid changed from orange to off-
white, as shown in Fig. 2. IR and 13C{1H} NMR spectra
of the product measured in the solid state revealed that
it contained a mixture of Rh complex with a carbonyl
ligand, A, and a smaller amount of 2a. Addition of Et2O
to the solid mixture did not cause dissolution of it, but
the solid recovered from the dispersion in Et2O was
composed of analytically pure 2a.
Fig. 3 shows change of the IR spectra of the product
of solid–gas reaction of CO with 1a measured in the
absorbance mode. Benzophenone was added as an in-
ternal standard to estimate relative intensity of the car-
bonyl peaks. After 15 min from the beginning, a small
peak appeared at 1979 cmꢀ1. The peak is at the same
position as that of 2a, although it is broadened signifi-
cantly compared with that of 2a prepared by the reac-
tion in toluene solution and purified by recrystallization.
After 30 min, growth of a peak at 1970 cmꢀ1 was ob-
served. Relative peak intensity of the product to that of
benzophenone (carbonyl stretching, 1659 cmꢀ1) indi-
cated that the peak growth was ceased at 60 min after
introducing CO. Thus, the reaction produces complex A
that exhibits m(CO) peak at lower wavenumber than 2a.
Similar solid–gas reactions of CO with 1b and with 1c
PMe
3
PMe
3
Me P Rh OC H -NO -4
+ CO
3
6
4
2
OC Rh OC H -NO -4 (3)
6 4 2
– PMe
3
PMe
3
PMe
3
3c
4c
ð3Þ
Fig. 1 shows molecular structures of 2a–2c and 4c
determined by X-ray crystallography. Selected bond

K. Osakada, H. Ishii / Inorganica Chimica Acta 357 (2004) 3007–3013
3009
Table 1
ꢀ
Selected bond distances (A) and angles (°)
2a
2b
2c
4c
Rh1–C1
Rh1–O2
Rh1–P1
Rh1–P2
C1–O1
1.829(6)
2.074(3)
2.324(1)
2.332(1)
1.129(5)
1.304(5)
1.807(4)
2.061(3)
2.322(2)
2.321(2)
1.145(4)
1.294(4)
1.829(9)
2.072(5)
2.335(2)
2.331(2)
1.127(9)
1.302(8)
1.790(6)
2.089(4)
2.312(2)
2.315(2)
1.154(7)
1.288(6)
O2–C2
P1–Rh1–P2
P1–Rh1–C1
P1–Rh1–O2
P2–Rh1–O2
P2–Rh1–C1
C1–Rh1–O2
Rh1–C1–O1
Rh1–O2–C2
174.81(5)
88.7(2)
92.1(1)
177.11(4)
89.9(1)
172.88(8)
90.9(2)
86.6(1)
177.49(7)
91.8(2)
89.1(1)
89.22(9)
93.03(9)
88.0(1)
89.4(1)
89.2(2)
94.8(1)
87.8(2)
88.5(1)
90.7(2)
172.8(2)
178.4(5)
135.0(3)
175.9(2)
178.9(4)
134.2(2)
177.0(3)
178.2(8)
130.5(4)
177.5(3)
178.0(6)
126.0(4)
Fig. 2. Change of color of 1a during the reaction with CO in the solid
state.
produce the complexes with the CO ligand as a yellow
paste and off-white solid, respectively. Fig. 4 shows
change of the IR spectrum during the reactions of CO
with 1b and with 1c. The peaks are observed at 1973 and
1975 cmꢀ1 which are different positions from Vaska-
type complexes 2b (1987 cmꢀ1) and 2c (1985 cmꢀ1). The
IR spectra of the products do not show the peak due to
Vaska-type complexes throughout the reaction.
Fig. 5 shows the CP/MAS 13C{1H} NMR spectrum
of the product of the solid–gas reaction of 13CO with 1a.
A peak at d 190 is assigned to the carbonyl ligand of 2b
formed via the solid–gas reaction and that formed dur-
ing the measurement at high temperature. A larger sig-
nal at d 274 is assigned to the complex A. The products
from the solid–gas reaction of 13CO with 1b and 1c ex-
hibit the signals at d 271 and 275, which are assigned to
B and C, respectively. These low magnetic field positions
of the carbonyl carbon are not ascribed to bridging
coordination of the carbonyl ligand but to low electron
density of the carbon of the intermediates in the solid
state because the IR frequencies at the CO stretching are
within the range of non-bridging carbonyl ligand.
Fig. 3. IR spectra of 1a during the solid–gas reaction with CO.
We tentatively assign the penta-coordinated structure
Rh(OAr)(CO)(PPh3)3 for the product of the solid–gas
reactions because it is converted into Vaska-type com-
plexes only by treating it with solvents. An ionic com-
plex [Rh(CO)(PPh3)3]þOArꢀ can be considered as the
structure. Further evidences for the structures of A–C
were not obtained. We examined a reaction of CO with
single crystals of 1a with expectation of the crystallo-
graphic study of the product, but the crystal lattices are
not kept after the reactions. Reaction of PPh3 with the
Vaska-type complex 2a does not cause change of the
complex at all.

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K. Osakada, H. Ishii / Inorganica Chimica Acta 357 (2004) 3007–3013
Fig. 6. IR spectra of 3c during the solid–gas reaction with CO.
days. These results indicate that the initially formed
complex D is turned into the final product 4c in the
solid state and that the Vaska-type complex of the
solid state reaction is formed via intermediate D. Low
vapor pressure of PMe3 seems to enhance the ligand
substitution.
Fig. 4. IR spectra of (a) 2a and (b) 2b during the solid–gas reaction
with CO.
In summary, the solid–gas reaction of carbon mon-
oxide with the aryloxide rhodium(I) complexes affords
the complexes that can be transformed easily by addi-
tion of solvent into Vaska-type complexes by addition of
solvent. The reactions are completed in a short period
(15–60 min), indicating that penetration of CO within
the solid and the chemical reaction in the solid state
occurs rapidly.
3. Experimental
3.1. General, measurements and materials
All the manipulations were performed under nitrogen
using standard Schlenk techniques. Solvents were dis-
tilled by usual method and stored under nitrogen. Other
organic chemicals were purchased and used as received.
[Rh(l-OAr)(cod)]2 (Ar ¼ C6Cl5, C6F5, C6H4–NO2-4)
were prepared from the reaction of ArOH with [Rh(l-
OMe)(cod)]2 [10] according to the literature describing
the preparation of [Rh(l-OPh)(cod)]2 [5,11]. IR spectra
were recorded on a JASCO-IR 810 spectrophotometer.
NMR spectra were obtained on JEOL EX-400 and
Varian Mercury 300 spectrometers. Elemental analyses
were carried out by a Yanagimoto Type MT-2 CHN
autocorder.
Fig. 5. CP/MAS 13C NMR spectrum of A (67.5 MHz).
Solid–gas carbonylation of 3c produces a mixture of
Vaska-type complex 4c and complex D, the latter of
which shows the IR peak at lower position (1933 cmꢀ1
than 4c (1962 cmꢀ1) at the initial stage of the reaction.
Fig. 6 shows change of the IR spectrum during the re-
action. After 5 days, the peak of D is observed in a
similar intensity to that of 4c. After 13 days, the ratio
becomes smaller, and the peak is not detected after 23
)

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3011
3.2. Preparation of Rh(OC6Cl5)(PPh3)3 (1a)
3.5. Reaction of CO with Rh(OC6Cl5)(PPh3)3 (1a) in
solution
To a toluene (10 ml) solution of [Rh(OC6Cl5)(cod)]2
(236 mg, 0.25 mmol) was added PPh3 (2.4 g, 9.2 mmol)
at room temperature. The initially yellow dispersion was
converted to an orange solution during heating the
mixture for 2 h at 60 °C. The solvent was removed under
vacuum. The produced solid was recrystallized from
Et2O–hexane to cause separation of an orange solid
from the solution. The solid was collected by filtration,
followed by washing with Et2O, and dried in vacuo to
afford 1a as deep orange microcrystals (123 mg, 53%).
1H NMR (CDCl3, 400 MHz, r.t.): d 7.45 (d, 6H, –
C6H5), 7.65 (t, J ¼ 6 Hz, 9H, –C6H5). 31P{1H} NMR
(benzene-d6, 160 MHz, r.t.): d 30.3 (dd, J(RhP) ¼ 133
Hz, J(PP) ¼ 39 Hz), 51.1 (dt, J(RhP) ¼ 199 Hz,
J(PP) ¼ 39 Hz).
Complex 1a (123 mg, 0.11 mmol) was dissolved in
toluene (3 ml) in a Schlenk flask (20 ml). After degassing
the system, CO (1 atm) was introduced, which caused
change of color of the solution from orange to yellow
soon. After 5 min, the solvent was removed by evapo-
ration. The obtained solid product was washed with
Et2O and dried in vacuo to give Rh(OC6Cl5)(CO)-
(PPh3)2 (2a) (65 mg, 67%). Recrystallization from THF/
hexane afforded yellow crystals. 31P{1H} NMR (CDCl3,
160 MHz, r.t.): d 30.5 (d, J(RhP) ¼ 137 Hz). IR (KBr
pellet): m(CO) 1979 cmꢀ1
.
Similar reactions of CO with 1b and with 1c in tolu-
ene solution afforded Rh(OC6F5)(CO)(PPh3)2 (2b)
(70%) and Rh(OC6H4–NO2-p)(CO)(PPh3)2 (2c) (76%),
respectively.
Data of 2b are as follows. 31P{1H} NMR (benzene-
d6, 121 MHz, r.t.): d 29.6 (d, J(RhP) ¼ 135 Hz). IR (KBr
pellet): m(CO) 1987 cmꢀ1. Anal. Calc. for C43H30-
F5O2P2Rh: C, 61.60; H, 3.61; F, 11.33. Found: C, 61.96;
H, 4.13; F, 10.97%.
3.3. Preparation of Rh(OC6F5)(PPh3)3 (1b)
To a toluene (10 ml) solution of [Rh(OC6F5)(cod)]2
(270 mg, 0.34 mmol) was added PPh3 (1.1 g, 4.1 mmol)
at room temperature. PPh3 was soon dissolved in the
solvent to form an orange solution. The solution was
stirred for 5 min at that temperature. The solvent was
removed by evaporation. The resulted solid was re-
crystallized from Et2O–hexane to give 1b as a yellow–
Data of 2c are as follows. 31P{1H} NMR (benzene-
d6, 121 MHz, r.t.): d 29.4 (d, J(RhP) ¼ 135 Hz). IR (KBr
pellet): m(CO) 1985 cmꢀ1
.
3.6. Preparation of Rh(OC6H4–NO2-p)(PMe3)3 (3c)
1
orange solid (309 mg, 84%). H NMR (benzene-d6, 300
Addition of PMe3 (0.5 ml, 4.8 mmol) to a toluene (10
ml) dispersion of [Rh(OC6H4–NO2-p)(cod)]2 (542 mg,
0.78 mmol) caused change of color of the reaction mixture
from yellow to orange. After stirring for 5 min, the solvent
was removed by evaporation. The obtained solid product
was washed with hexane and dried in vacuo to give 3c as a
deep yellow solid (840 mg, 100%). 31P{1H} NMR (ben-
zene-d6, 160 MHz, r.t.): d )8.2 (dd, J(RhP) ¼ 86 Hz,
J(PP) ¼ 27 Hz), 5.2 (dt, J(RhP) ¼ 113 Hz, J(PP) ¼ 27 Hz).
Anal. Calc. for C15H31NO3P3Rh: C, 38.40; H, 6.66; N,
2.98. Found: C, 38.14; H, 6.94; N, 2.85%.
MHz, r.t.): d 6.85 (d, 6H, –C6H5), 7.73 (t, J ¼ 7 Hz,
9H, –C6H5). 31P{1H} NMR (benzene-d6, 121 MHz,
r.t.): d 32.0 (dd, J(RhP) ¼ 148 Hz, J(PP) ¼ 41 Hz), 55.2
(dt, J(RhP) ¼ 184 Hz, J(PP) ¼ 41 Hz). Anal. Calc. for
C60H45F5OP3Rh: C, 67.17; H, 4.23; F, 8.85. Found: C,
67.23; H, 4.43; F, 7.88%.
3.4. Preparation of Rh(OC6H4–NO2-p)(PPh3)3 (1c)
To a toluene (10 ml) solution of [Rh(OC6H4–NO2-
p)(cod)]2 (153 mg, 0.22 mmol) was added PPh3 (604
mg, 2.6 mmol) at room temperature. PPh3 was soon
dissolved to form an orange solution. After stirring
the solution for 5 min, the solvent was removed by
evaporation. The obtained solid was washed with
Et2O and dried in vacuo to give 1c as yellow–orange
crystals (369 mg, 79%). Recrystallization from THF/
3.7. Reaction of CO with Rh(OC6H4–NO2-p)(PMe3)3
(3c) in solution
A solution of Rh(OC6H4–NO2-p)(PMe3)3 (3c) (34
mg, 0.072 mmol) in toluene (3 ml) was prepared in a
Schlenk flask (20 ml). After degassing the system, CO (1
atm) was introduced at room temperature. The solution
was soon turned from orange to yellow. After 5 min, the
solvent was removed by evaporation. The obtained solid
was washed with Et2O and hexane, and dried in vacuo
to afford Rh(OC6H4–NO2-p)(CO)(PMe3)2 (4c) (19 mg,
62%). Recrystallization from acetone/hexane afforded
yellow single crystals.
1
hexane afforded single crystals. H NMR (benzene-d6,
300 MHz, r.t.): d 6.43 (d, 2H, –C6H4NO2-p), 6.80 (d,
6H, –C6H5), 7.56 (t, J ¼ 6 Hz, 9H, –C6H5), 8.16 (d,
2H, –C6H4NO2-p). 31P{1H} NMR (benzene-d6, 160
MHz, r.t.): d 31.6 (dd, J(RhP) ¼ 153 Hz, J(PP) ¼ 39
Hz), 51.0 (dt, J(RhP) ¼ 176 Hz, J(PP) ¼ 39 Hz). Anal.
Calc. for C60H49NO3P3Rh: C, 70.11; H, 4.80; N, 1.36.
Found: C, 69.91; H, 6.26; N, 1.57%.
31P{1H} NMR (CDCl3, 160 MHz, r.t.): d )8.4 (d,
J(RhP) ¼ 121 Hz). IR (KBr pellet): m(CO) 1964 cmꢀ1
.

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Anal. Calc. for C13H22NO4P2Rh: C, 37.07; H, 5.26; N,
3.33. Found: C, 37.03; H, 5.38; N, 3.20%.
ane (10 ml) to give 2b as a yellow solid (27 mg, 80%).
31P{1H} NMR (benzene-d6, 121 MHz, r.t.): d 29.6 (d,
J(RhP) ¼ 135 Hz). 13C{1H} NMR (CD2Cl2, 125 MHz,
25 °C): d 189.93 (d, J(RhC) ¼ 66 Hz, J(PC) was not ob-
served due to peak broadening). IR (KBr pellet): m(CO)
1987 cmꢀ1. Anal. Calc. for C43H30F5O2P2Rh: C, 61.60;
H, 3.61; F, 11.33. Found: C, 61.87; H, 3.87; F, 11.53%.
3.8. Solid–gas reaction of CO with Rh(OC6Cl5)(PPh3)3 (1a)
Rh(OC6Cl5)(PPh3)3 (1a) (335 mg, 0.29 mmol) was
transferred to a Schlenk flask (20 ml). After degassing,
CO (1 atm) was introduced. The orange solid was
gradually turned to off-white. The solid product was
composed of A and 2a based on the IR and CP/MAS
13C{1H} NMR spectra.
3.10. Solid–gas reaction of CO with Rh(OC6H4–NO2-
p)(PPh3)3 (1c)
A Schlenk flask (20 ml) containing Rh(OC6H4–NO2-
p)(PPh3)3 (1c) (8 mg, 0.01 mmol) was degassed at room
temperature. Introducing CO (1 atm) at room tempera-
ture turned the orange solid to form an off-white solid C.
The solid product C was recrystallized from Et2O(2
ml)/hexane(10 ml) to give 2b as a yellow solid (6.7 mg,
85%). 31P{1H} NMR (benzene-d6, 121 MHz, r.t.): d 29.4
(d, J (RhP) ¼ 135 Hz). 13C{1H} NMR (CD2Cl2, 125
MHz, 25 °C): d 189.60 (d, J(RhC) ¼ 70 Hz, J(PC) was not
observed due to peak broadening). IR (KBr pellet): m(CO)
1985 cmꢀ1. Anal. Calc. for C43H34NO4P2Rh: C, 65.08; H,
4.32; N, 1.76. Found: C, 64.95; H, 4.51; N, 1.70%.
The product was washed with Et2O and dried in vacuo
to give 2a as a yellow solid (208 mg, 79%). IR (KBr pel-
let): m(CO) 1979 cmꢀ1 13C{1H} NMR (CD2Cl2, 125
.
MHz, )70 °C): d 190.07 (dt, J(RhC) ¼ 70 Hz, J(PC) ¼ 18
Hz), 136.94, 136.83, 134.57, 133.80 (d, J ¼ 27 Hz),
133.69, 131.17, 130.94, 130.73, 130.62, 129.05, 128.79,
128.71, 128.61. 128.43, 121.07. 31P{1H} NMR (CDCl3,
160 MHz, r.t.): d 30.5 (d, J (RhP) ¼ 137 Hz). 31P{1H}
NMR (13CO-enriched sample, CD2Cl2, 160 MHz, )70
°C): d 34.2 (d, J(RhP) ¼ 135 Hz, J(CP) ¼ 18 Hz). Anal.
Calc. for C43H30Cl5O2P2Rh: C, 56.09; H, 3.28; Cl, 19.25.
Found: C, 55.88; H, 3.94; Cl, 18.73%.
3.11. Solid–gas reaction of PPh3 with Rh(OC6Cl5)
(CO)(PPh3)2 (3a)
3.9. Solid–gas reaction of CO with Rh(OC6F5)(PPh3)3 (1b)
A Schlenk flask (20 ml) containing 1b (39 mg, 0.036
mmol) was evacuated by vacuum pump. CO (1 atm) was
introduced to the flask at room temperature. Yellow or-
ange solid was gradually turned into a yellow paste (B).
The product B was recrystallized from Et2O (2 ml)/hex-
Finely ground PPh3 (30 mg, 0.11 mmol) was mixed
with complex 3a (30 mg, 0.026 mmol) at room temper-
ature. The IR peak at 1979 cmꢀ1 did not change even
after 5 days. Analogous reaction of CO with A without
solvent did not cause change of the IR peaks.
Table 2
Crystal data and details of structure refinement
2a
2b
2c
4c
Formula
C
920.83
43H30Cl5O2P2Rh
C43H30F5O2P2Rh
838.56
triclinic
C43H34NO4P2Rh
793.60
C13H22NO4P2Rh
421.18
Molecular weight
Crystal system
Space group
monoclinic
P21=n (no. 14)
13.304(3)
19.713(6)
15.641(3)
monoclinic
P21=n (No. 14)
15.748(4)
monoclinic
P21=n (no. 14)
6.018(3)
ꢁ
P1 (no. 2)
ꢀ
a (A)
12.810(9)
14.117(8)
11.899(7)
92.00(5)
113.99(5)
74.22(5)
1885
ꢀ
b (A)
14.701(4)
17.414(3)
18.247(4)
16.428(3)
ꢀ
c (A)
a (°)
b (°)
c (°)
106.49(1)
112.92(1)
92.67(3)
3
ꢀ
V (A )
3933
4
3714
4
1802
4
Z
2
0.598
l (cmꢀ1
)
0.891
1856
0.589
1624
1.235
1024
F (0 0 0)
Dcalcd (g cmꢀ3
Crystal size (mm)
848
1.477
)
1.555
0.5 ꢁ 0.3 ꢁ 0.2
5.0–55.0
9299
1.419
0.2 ꢁ 0.2 ꢁ 0.2
5.0–55.0
8866
1.833
0.3 ꢁ 0.1 ꢁ 0.1
5.0–55.0
4273
0.7 ꢁ 0.5 ꢁ 0.3
5.0–50.0
8673
2h range (°)
Number of unique reflectionsa
Number of used reflections
Number of variables
R
5699
478
6460
478
2845
460
2378
190
0.041
0.034
2.26
0.042
0.038
2.94
0.061
0.050
2.29
0.041
0.031
1.74
Rw
Goodness-of-fit
a I > 3rðIÞ.

K. Osakada, H. Ishii / Inorganica Chimica Acta 357 (2004) 3007–3013
3013
3.12. Solid–gas reaction of CO with Rh(OC6H4–NO2-p)-
(PMe3)3 (3c)
References
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caused change of deep yellow solid to a pale yellow
solid. After 5 days, the product is a mixture of 4c and D
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This work was financially supported by a Grant-in-
aid for Scientific Research from the Ministry of Edu-
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